Simulation studies of structure and edge tension of lipid bilayer edges: effects of tail structure and force-field.

PubMed

West, Ana; Ma, Kevin; Chung, Jonathan L; Kindt, James T

2013-08-15

Molecular dynamics simulations of lipid bilayer ribbons have been performed to investigate the structures and line tensions associated with free bilayer edges. Simulations carried out for dioleoyl phosphatidylcholine with three different force-field parameter sets yielded edge line tensions of 45 ± 2 pN, over 50% greater than the most recently reported experimentally determined value for this lipid. Edge tensions obtained from simulations of a series of phosphatidylcholine lipid bilayer ribbons with saturated acyl tails of length 12-16 carbons and with monounsaturated acyl tails of length 14-18 carbons could be correlated with the excess area associated with forming the edge, through a two-parameter fit. Saturated-tail lipids underwent local thickening near the edge, producing denser packing that correlated with lower line tensions, while unsaturated-tail lipids showed little or no local thickening. In a dipalmitoyl phosphatidylcholine ribbon initiated in a tilted gel-phase structure, lipid headgroups tended to tilt toward the nearer edge producing a herringbone pattern, an accommodation that may account for the reported edge-induced stabilization of an ordered structure at temperatures near a lipid gel-fluid phase transition.

Permeability and electrical properties of planar lipid membranes from thylakoid lipids.

PubMed Central

Fuks, B; Homblé, F

1994-01-01

Electrical measurements were carried out on planar lipid membranes from thylakoid lipids. The specific capacitance of membranes formed from decane-containing monogalactosyldiacylglycerol (MGDG), which accounts for 57% of the total lipid content of thylakoids, showed that it adopted a bilayer structure. Solvent-free bilayers of MGDG were not formed, with very rare exceptions, indicating that decane is required to stabilize the planar conformation. However, this cone-shaped lipid produces bilayer structures in combination with other cylindrical thylakoid lipids even in the absence of organic solvent. We compared the properties of solvent-free and decane-containing bilayers from MGDG, soybean lecithin, and the quaternary mixture of lipids similar to that found in vivo. The conductance of decane-MGDG was 26 times higher than that of decane-lecithin. The flux through the decane-lecithin bilayer was found to be slightly dependent on pH, whereas the decane-MGDG membrane was not. The specific conductance of bilayers formed from the quaternary mixture of lipids was 5 to 10 times larger than lecithin (with alkane or not). Further experiments with bilayers made in the presence of a KCl gradient showed that decane-MGDG, decane-MGDG/DGDG/SQDG/PG, and solvent-free MGDG/DGDG/SQDG/PG were cation-selective. The permeability coefficient for potassium ranged from 4.9 to 8.3 x 10(-11) cm s-1. The permeability coefficient for protons in galactolipids, however, was determined to be about six orders of magnitude higher than the value for potassium ions. The HCl permeation mechanism through the lipid membranes was determined from diffusion potentials measured in HCl gradients. Our results suggest that HCl was not transported as neutral molecules. The data is discussed with regard to the function of galactolipids in the ion transport through thylakoid membranes. PMID:8061192

Mechanism of unassisted ion transport across membrane bilayers

NASA Technical Reports Server (NTRS)

Wilson, M. A.; Pohorille, A.

1996-01-01

To establish how charged species move from water to the nonpolar membrane interior and to determine the energetic and structural effects accompanying this process, we performed molecular dynamics simulations of the transport of Na+ and Cl- across a lipid bilayer located between two water lamellae. The total length of molecular dynamics trajectories generated for each ion was 10 ns. Our simulations demonstrate that permeation of ions into the membrane is accompanied by the formation of deep, asymmetric thinning defects in the bilayer, whereby polar lipid head groups and water penetrate the nonpolar membrane interior. Once the ion crosses the midplane of the bilayer the deformation "switches sides"; the initial defect slowly relaxes, and a defect forms in the outgoing side of the bilayer. As a result, the ion remains well solvated during the process; the total number of oxygen atoms from water and lipid head groups in the first solvation shell remains constant. A similar membrane deformation is formed when the ion is instantaneously inserted into the interior of the bilayer. The formation of defects considerably lowers the free energy barrier to transfer of the ion across the bilayer and, consequently, increases the permeabilities of the membrane to ions, compared to the rigid, planar structure, by approximately 14 orders of magnitude. Our results have implications for drug delivery using liposomes and peptide insertion into membranes.

Modulation of KvAP Unitary Conductance and Gating by 1-Alkanols and Other Surface Active Agents

PubMed Central

Finol-Urdaneta, Rocio K.; McArthur, Jeffrey R.; Juranka, Peter F.; French, Robert J.; Morris, Catherine E.

2010-01-01

Abstract The actions of alcohols and anesthetics on ion channels are poorly understood. Controversy continues about whether bilayer restructuring is relevant to the modulatory effects of these surface active agents (SAAs). Some voltage-gated K channels (Kv), but not KvAP, have putative low affinity alcohol-binding sites, and because KvAP structures have been determined in bilayers, KvAP could offer insights into the contribution of bilayer mechanics to SAA actions. We monitored KvAP unitary conductance and macroscopic activation and inactivation kinetics in PE:PG/decane bilayers with and without exposure to classic SAAs (short-chain 1-alkanols, cholesterol, and selected anesthetics: halothane, isoflurane, chloroform). At levels that did not measurably alter membrane specific capacitance, alkanols caused functional changes in KvAP behavior including lowered unitary conductance, modified kinetics, and shifted voltage dependence for activation. A simple explanation is that the site of SAA action on KvAP is its entire lateral interface with the PE:PG/decane bilayer, with SAA-induced changes in surface tension and bilayer packing order combining to modulate the shape and stability of various conformations. The KvAP structural adjustment to diverse bilayer pressure profiles has implications for understanding desirable and undesirable actions of SAA-like drugs and, broadly, predicts that channel gating, conductance and pharmacology may differ when membrane packing order differs, as in raft versus nonraft domains. PMID:20197029

The Structure of the Mouse Serotonin 5-HT3 Receptor in Lipid Vesicles.

PubMed

Kudryashev, Mikhail; Castaño-Díez, Daniel; Deluz, Cédric; Hassaine, Gherici; Grasso, Luigino; Graf-Meyer, Alexandra; Vogel, Horst; Stahlberg, Henning

2016-01-05

The function of membrane proteins is best understood if their structure in the lipid membrane is known. Here, we determined the structure of the mouse serotonin 5-HT3 receptor inserted in lipid bilayers to a resolution of 12 Å without stabilizing antibodies by cryo electron tomography and subtomogram averaging. The reconstruction reveals protein secondary structure elements in the transmembrane region, the extracellular pore, and the transmembrane channel pathway, showing an overall similarity to the available X-ray model of the truncated 5-HT3 receptor determined in the presence of a stabilizing nanobody. Structural analysis of the 5-HT3 receptor embedded in a lipid bilayer allowed the position of the membrane to be determined. Interactions between the densely packed receptors in lipids were visualized, revealing that the interactions were maintained by the short horizontal helices. In combination with methodological improvements, our approach enables the structural analysis of membrane proteins in response to voltage and ligand gating. Copyright © 2016 Elsevier Ltd. All rights reserved.

Challenges in the Development of Functional Assays of Membrane Proteins

PubMed Central

Tiefenauer, Louis; Demarche, Sophie

2012-01-01

Lipid bilayers are natural barriers of biological cells and cellular compartments. Membrane proteins integrated in biological membranes enable vital cell functions such as signal transduction and the transport of ions or small molecules. In order to determine the activity of a protein of interest at defined conditions, the membrane protein has to be integrated into artificial lipid bilayers immobilized on a surface. For the fabrication of such biosensors expertise is required in material science, surface and analytical chemistry, molecular biology and biotechnology. Specifically, techniques are needed for structuring surfaces in the micro- and nanometer scale, chemical modification and analysis, lipid bilayer formation, protein expression, purification and solubilization, and most importantly, protein integration into engineered lipid bilayers. Electrochemical and optical methods are suitable to detect membrane activity-related signals. The importance of structural knowledge to understand membrane protein function is obvious. Presently only a few structures of membrane proteins are solved at atomic resolution. Functional assays together with known structures of individual membrane proteins will contribute to a better understanding of vital biological processes occurring at biological membranes. Such assays will be utilized in the discovery of drugs, since membrane proteins are major drug targets.

Molecular dynamics of individual alpha-helices of bacteriorhodopsin in dimyristol phosphatidylocholine. I. Structure and dynamics.

PubMed

Woolf, T B

1997-11-01

Understanding the role of the lipid bilayer in membrane protein structure and dynamics is needed for tertiary structure determination methods. However, the molecular details are not well understood. Molecular dynamics computer calculations can provide insight into these molecular details of protein:lipid interactions. This paper reports on 10 simulations of individual alpha-helices in explicit lipid bilayers. The 10 helices were selected from the bacteriorhodopsin structure as representative alpha-helical membrane folding components. The bilayer is constructed of dimyristoyl phosphatidylcholine molecules. The only major difference between simulations is the primary sequence of the alpha-helix. The results show dramatic differences in motional behavior between alpha-helices. For example, helix A has much smaller root-mean-squared deviations than does helix D. This can be understood in terms of the presence of aromatic residues at the interface for helix A that are not present in helix D. Additional motions are possible for the helices that contain proline side chains relative to other amino acids. The results thus provide insight into the types of motion and the average structures possible for helices within the bilayer setting and demonstrate the strength of molecular simulations in providing molecular details that are not directly visualized in experiments.

Confocal Raman Microscopy for in Situ Measurement of Phospholipid-Water Partitioning into Model Phospholipid Bilayers within Individual Chromatographic Particles.

PubMed

Kitt, Jay P; Bryce, David A; Minteer, Shelley D; Harris, Joel M

2018-06-05

The phospholipid-water partition coefficient is a commonly measured parameter that correlates with drug efficacy, small-molecule toxicity, and accumulation of molecules in biological systems in the environment. Despite the utility of this parameter, methods for measuring phospholipid-water partition coefficients are limited. This is due to the difficulty of making quantitative measurements in vesicle membranes or supported phospholipid bilayers, both of which are small-volume phases that challenge the sensitivity of many analytical techniques. In this work, we employ in situ confocal Raman microscopy to probe the partitioning of a model membrane-active compound, 2-(4-isobutylphenyl) propionic acid or ibuprofen, into both hybrid- and supported-phospholipid bilayers deposited on the pore walls of individual chromatographic particles. The large surface-area-to-volume ratio of chromatographic silica allows interrogation of a significant lipid bilayer area within a very small volume. The local phospholipid concentration within a confocal probe volume inside the particle can be as high as 0.5 M, which overcomes the sensitivity limitations of making measurements in the limited membrane areas of single vesicles or planar supported bilayers. Quantitative determination of ibuprofen partitioning is achieved by using the phospholipid acyl-chains of the within-particle bilayer as an internal standard. This approach is tested for measurements of pH-dependent partitioning of ibuprofen into both hybrid-lipid and supported-lipid bilayers within silica particles, and the results are compared with octanol-water partitioning and with partitioning into individual optically trapped phospholipid vesicle membranes. Additionally, the impact of ibuprofen partitioning on bilayer structure is evaluated for both within-particle model membranes and compared with the structural impacts of partitioning into vesicle lipid bilayers.

Laser Fabrication of Polymer Ferroelectric Nanostructures for Nonvolatile Organic Memory Devices.

PubMed

Martínez-Tong, Daniel E; Rodríguez-Rodríguez, Álvaro; Nogales, Aurora; García-Gutiérrez, Mari-Cruz; Pérez-Murano, Francesc; Llobet, Jordi; Ezquerra, Tiberio A; Rebollar, Esther

2015-09-09

Polymer ferroelectric laser-induced periodic surface structures (LIPSS) have been prepared on ferroelectric thin films of a poly(vinylidene fluoride-trifluoroethylene) copolymer. Although this copolymer does not absorb light at the laser wavelength, LIPSS on the copolymer can be obtained by forming a bilayer with other light-absorbing polymers. The ferroelectric nature of the structured bilayer was proven by piezoresponse force microscopy measurements. Ferroelectric hysteresis was found on both the bilayer and the laser-structured bilayer. We show that it is possible to write ferroelectric information at the nanoscale. The laser-structured ferroelectric bilayer showed an increase in the information storage density of an order of magnitude, in comparison to the original bilayer.

Structural characterization of the voltage sensor domain and voltage-gated K+- channel proteins vectorially-oriented within a single bilayer membrane at the solid/vapor and solid/liquid interfaces via neutron interferometry

PubMed Central

Gupta, S.; Dura, J.A.; Freites, J.A.; Tobias, D.J.; Blasie, J. K.

2012-01-01

The voltage-sensor domain (VSD) is a modular 4-helix bundle component that confers voltage sensitivity to voltage-gated cation channels in biological membranes. Despite extensive biophysical studies and the recent availability of x-ray crystal structures for a few voltage-gated potassium (Kv-) channels and a voltage-gate sodium (Nav-) channel, a complete understanding of the cooperative mechanism of electromechanical coupling, interconverting the closed-to-open states (i.e. non-conducting to cation conducting) remains undetermined. Moreover, the function of these domains is highly dependent on the physical-chemical properties of the surrounding lipid membrane environment. The basis for this work was provided by a recent structural study of the VSD from a prokaryotic Kv-channel vectorially-oriented within a single phospholipid (POPC; 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine) membrane investigated by x-ray interferometry at the solid/moist He (or solid/vapor) and solid/liquid interfaces thus achieving partial to full hydration, respectively (Gupta et. al. Phys. Rev E. 2011, 84). Here, we utilize neutron interferometry to characterize this system in substantially greater structural detail at the sub-molecular level, due to its inherent advantages arising from solvent contrast variation coupled with the deuteration of selected sub-molecular membrane components, especially important for the membrane at the solid/liquid interface. We demonstrate the unique vectorial orientation of the VSD and the retention of its molecular conformation manifest in the asymmetric profile structure of the protein within the profile structure of this single bilayer membrane system. We definitively characterize the asymmetric phospholipid bilayer solvating the lateral surfaces of the VSD protein within the membrane. The profile structures of both the VSD protein and phospholipid bilayer depend upon the hydration state of the membrane. We also determine the distribution of water and exchangeable hydrogen throughout the profile structure of both the VSD itself and the VSD:POPC membrane. These two experimentally-determined water and exchangeable hydrogen distribution profiles are in good agreement with molecular dynamics simulations of the VSD protein vectorially-oriented within a fully hydrated POPC bilayer membrane, supporting the existence of the VSD’s water pore. This approach was extended to the full-length Kv-channel (KvAP) at solid/liquid interface, providing the separate profile structures of the KvAP protein and the POPC bilayer within the reconstituted KvAP:POPC membrane. PMID:22686684

Time-resolved distance determination by tryptophan fluorescence quenching: probing intermediates in membrane protein folding.

PubMed

Kleinschmidt, J H; Tamm, L K

1999-04-20

The mechanism of insertion and folding of an integral membrane protein has been investigated with the beta-barrel forming outer membrane protein A (OmpA) of Escherichia coli. This work describes a new approach to this problem by combining structural information obtained from tryptophan fluorescence quenching at different depths in the lipid bilayer with the kinetics of the refolding process. Experiments carried out over a temperature range between 2 and 40 degrees C allowed us to detect, trap, and characterize previously unidentified folding intermediates on the pathway of OmpA insertion and folding into lipid bilayers. Three membrane-bound intermediates were found in which the average distances of the Trps were 14-16, 10-11, and 0-5 A, respectively, from the bilayer center. The first folding intermediate is stable at 2 degrees C for at least 1 h. A second intermediate has been isolated at temperatures between 7 and 20 degrees C. The Trps move 4-5 A closer to the center of the bilayer at this stage. Subsequently, in an intermediate that is observable at 26-28 degrees C, the Trps move another 5-10 A closer to the center of the bilayer. The final (native) structure is observed at higher temperatures of refolding. In this structure, the Trps are located on average about 9-10 A from the bilayer center. Monitoring the evolution of Trp fluorescence quenching by a set of brominated lipids during refolding at various temperatures therefore allowed us to identify and characterize intermediate states in the folding process of an integral membrane protein.

Nanoporous microbead supported bilayers: stability, physical characterization, and incorporation of functional transmembrane proteins.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, Ryan W.; Brozik, James A.; Brozik, Susan Marie

2007-03-01

The introduction of functional transmembrane proteins into supported bilayer-based biomimetic systems presents a significant challenge for biophysics. Among the various methods for producing supported bilayers, liposomal fusion offers a versatile method for the introduction of membrane proteins into supported bilayers on a variety of substrates. In this study, the properties of protein containing unilamellar phosphocholine lipid bilayers on nanoporous silica microspheres are investigated. The effects of the silica substrate, pore structure, and the substrate curvature on the stability of the membrane and the functionality of the membrane protein are determined. Supported bilayers on porous silica microspheres show a significant increasemore » in surface area on surfaces with structures in excess of 10 nm as well as an overall decrease in stability resulting from increasing pore size and curvature. Comparison of the liposomal and detergent-mediated introduction of purified bacteriorhodopsin (bR) and the human type 3 serotonin receptor (5HT3R) are investigated focusing on the resulting protein function, diffusion, orientation, and incorporation efficiency. In both cases, functional proteins are observed; however, the reconstitution efficiency and orientation selectivity are significantly enhanced through detergent-mediated protein reconstitution. The results of these experiments provide a basis for bulk ionic and fluorescent dye-based compartmentalization assays as well as single-molecule optical and single-channel electrochemical interrogation of transmembrane proteins in a biomimetic platform.« less

Structure and magnetic properties of mono- and bi-layer graphene films on ultraprecision figured 4H-SiC(0001) surfaces.

PubMed

Hattori, Azusa N; Okamoto, Takeshi; Sadakuni, Shun; Murata, Junji; Oi, Hideo; Arima, Kenta; Sano, Yasuhisa; Hattori, Ken; Daimon, Hiroshi; Endo, Katsuyoshi; Yamauchi, Kazuto

2011-04-01

Monolayer and bilayer graphene films with a few hundred nm domain size were grown on ultraprecision figured 4H-SiC(0001) on-axis and 8 degrees -off surfaces by annealing in ultra-high vacuum. Using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, reflection high-energy electron diffraction, low-energy electron diffraction (LEED), Raman spectroscopy, and scanning tunneling microscopy, we investigated the structure, number of graphene layers, and chemical bonding of the graphene surfaces. Moreover, the magnetic property of the monolayer graphene was studied using in-situ surface magneto-optic Kerr effect at 40 K. LEED spots intensity distribution and XPS spectra for monolayer and bilayer graphene films could become an obvious and accurate fingerprint for the determination of graphene film thickness on SiC surface.

Structural Significance of Lipid Diversity as Studied by Small Angle Neutron and X-ray Scattering

DOE PAGES

Kučerka, Norbert; Heberle, Frederick A.; Pan, Jianjun; ...

2015-09-21

In this paper, we review recent developments in the rapidly growing field of membrane biophysics, with a focus on the structural properties of single lipid bilayers determined by different scattering techniques, namely neutron and X-ray scattering. The need for accurate lipid structural properties is emphasized by the sometimes conflicting results found in the literature, even in the case of the most studied lipid bilayers. Increasingly, accurate and detailed structural models require more experimental data, such as those from contrast varied neutron scattering and X-ray scattering experiments that are jointly refined with molecular dynamics simulations. This experimental and computational approach producesmore » robust bilayer structural parameters that enable insights, for example, into the interplay between collective membrane properties and its components (e.g., hydrocarbon chain length and unsaturation, and lipid headgroup composition). Finally, from model studies such as these, one is better able to appreciate how a real biological membrane can be tuned by balancing the contributions from the lipid’s different moieties (e.g., acyl chains, headgroups, backbones, etc.).« less

Confocal Raman Microscopy for In-situ Measurement of Phospholipid-Water Partitioning into Model Phospholipid Bilayers within Individual Chromatographic Particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kitt, Jay P.; Bryce, David A.; Minteer, Shelley D.

The phospholipid-water partition coefficient is a commonly measured parameter that correlates with drug efficacy, small-molecule toxicity, and accumulation of molecules in biological systems in the environment. Despite the utility of this parameter, methods for measuring phospholipid-water partition coefficients are limited. This is due to the difficulty of making quantitative measurements in vesicle membranes or supported phospholipid bilayers, both of which are small-volume phases that challenge the sensitivity of many analytical techniques. In this paper, we employ in-situ confocal Raman microscopy to probe the partitioning of a model membrane-active compound, 2-(4-isobutylphenyl) propionic acid or ibuprofen, into both hybrid- and supported-phospholipid bilayersmore » deposited on the pore walls of individual chromatographic particles. The large surface-area-to-volume ratio of chromatographic silica allows interrogation of a significant lipid bilayer area within a very small volume. The local phospholipid concentration within a confocal probe volume inside the particle can be as high as 0.5 M, which overcomes the sensitivity limitations of making measurements in the limited membrane areas of single vesicles or planar supported bilayers. Quantitative determination of ibuprofen partitioning is achieved by using the phospholipid acyl-chains of the within-particle bilayer as an internal standard. This approach is tested for measurements of pH-dependent partitioning of ibuprofen into both hybrid-lipid and supported-lipid bilayers within silica particles, and the results are compared with octanol-water partitioning and with partitioning into individual optically-trapped phospholipid vesicle membranes. Finally and additionally, the impact of ibuprofen partitioning on bilayer structure is evaluated for both within-particle model membranes and compared with the structural impacts of partitioning into vesicle lipid bilayers.« less

Confocal Raman Microscopy for In-situ Measurement of Phospholipid-Water Partitioning into Model Phospholipid Bilayers within Individual Chromatographic Particles

DOE PAGES

Kitt, Jay P.; Bryce, David A.; Minteer, Shelley D.; ...

2018-05-14

The phospholipid-water partition coefficient is a commonly measured parameter that correlates with drug efficacy, small-molecule toxicity, and accumulation of molecules in biological systems in the environment. Despite the utility of this parameter, methods for measuring phospholipid-water partition coefficients are limited. This is due to the difficulty of making quantitative measurements in vesicle membranes or supported phospholipid bilayers, both of which are small-volume phases that challenge the sensitivity of many analytical techniques. In this paper, we employ in-situ confocal Raman microscopy to probe the partitioning of a model membrane-active compound, 2-(4-isobutylphenyl) propionic acid or ibuprofen, into both hybrid- and supported-phospholipid bilayersmore » deposited on the pore walls of individual chromatographic particles. The large surface-area-to-volume ratio of chromatographic silica allows interrogation of a significant lipid bilayer area within a very small volume. The local phospholipid concentration within a confocal probe volume inside the particle can be as high as 0.5 M, which overcomes the sensitivity limitations of making measurements in the limited membrane areas of single vesicles or planar supported bilayers. Quantitative determination of ibuprofen partitioning is achieved by using the phospholipid acyl-chains of the within-particle bilayer as an internal standard. This approach is tested for measurements of pH-dependent partitioning of ibuprofen into both hybrid-lipid and supported-lipid bilayers within silica particles, and the results are compared with octanol-water partitioning and with partitioning into individual optically-trapped phospholipid vesicle membranes. Finally and additionally, the impact of ibuprofen partitioning on bilayer structure is evaluated for both within-particle model membranes and compared with the structural impacts of partitioning into vesicle lipid bilayers.« less

Effect of Membrane Tension on the Electric Field and Dipole Potential of Lipid Bilayer Membrane

PubMed Central

Warshaviak, Dora Toledo; Muellner, Michael J.; Chachisvilis, Mirianas

2011-01-01

The dipole potential of lipid bilayer membrane controls the difference in permeability of the membrane to oppositely charged ions. We have combined molecular dynamics (MD) simulations and experimental studies to determine changes in electric field and electrostatic potential of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) lipid bilayer in response to applied membrane tension. MD simulations based on CHARMM36 force field showed that electrostatic potential of DOPC bilayer decreases by ~45 mV in the physiologically relevant range of membrane tension values (0 to 15 dyn/cm). The electrostatic field exhibits a peak (~0.8×109 V/m) near the water/lipid interface which shifts by 0.9 Å towards the bilayer center at 15 dyn/cm. Maximum membrane tension of 15 dyn/cm caused 6.4% increase in area per lipid, 4.7% decrease in bilayer thickness and 1.4% increase in the volume of the bilayer. Dipole-potential sensitive fluorescent probes were used to detect membrane tension induced changes in DOPC vesicles exposed to osmotic stress. Experiments confirmed that dipole potential of DOPC bilayer decreases at higher membrane tensions. These results are suggestive of a potentially new mechanosensing mechanism by which mechanically induced structural changes in the lipid bilayer membrane could modulate the function of membrane proteins by altering electrostatic interactions and energetics of protein conformational states. PMID:21722624

Physicochemical properties of liposomes as potential anticancer drugs carriers. Interaction of etoposide and cytarabine with the membrane: Spectroscopic studies

NASA Astrophysics Data System (ADS)

Pentak, Danuta

2014-03-01

The interactions between etoposide, cytarabine and 1,2-dihexadecanoyl-sn-glycerol-3-phosphocholine bilayers were studied using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR). These techniques have proven to be a very powerful tool in studying the structure and dynamics of phospholipid bilayers. In particular, DSC can provide information on the phase transition temperature and cooperativity of the lipid molecules in the absence and presence of the drug. Vibrational spectroscopy is well suited to the study of drug-lipid interactions, since it allows for an investigation of the conformation of phospholipid molecules at different levels in lipid bilayers and follows structural changes that occur during the gel to liquid-crystalline phase transition. NMR supported the determination of the main phase transition temperatures (TC) of 1,2-dihexadecanoyl-sn-glycerol-3-phosphocholine (DPPC). The main phase transition temperature (TC) determined by 1H NMR is comparable with values obtained by DSC for all studied liposomes. The location of cytarabine and etoposide in liposomes was also determined by NMR. Atomic force microscopy (AFM) images, acquired immediately after sample deposition on a mica surface, revealed the spherical shape of lipid vesicles.

Solvent-assisted lipid bilayer formation on silicon dioxide and gold.

PubMed

Tabaei, Seyed R; Choi, Jae-Hyeok; Haw Zan, Goh; Zhdanov, Vladimir P; Cho, Nam-Joon

2014-09-02

Planar lipid bilayers on solid supports mimic the fundamental structure of biological membranes and can be investigated using a wide range of surface-sensitive techniques. Despite these advantages, planar bilayer fabrication is challenging, and there are no simple universal methods to form such bilayers on diverse material substrates. One of the novel methods recently proposed and proven to form a planar bilayer on silicon dioxide involves lipid deposition in organic solvent and solvent exchange to influence the phase of adsorbed lipids. To scrutinize the specifics of this solvent-assisted lipid bilayer (SALB) formation method and clarify the limits of its applicability, we have developed a simplified, continuous solvent-exchange version to form planar bilayers on silicon dioxide, gold, and alkanethiol-coated gold (in the latter case, a lipid monolayer is formed to yield a hybrid bilayer) and varied the type of organic solvent and rate of solvent exchange. By tracking the SALB formation process with simultaneous quartz crystal microbalance-dissipation (QCM-D) and ellipsometry, it was determined that the acoustic, optical, and hydration masses along with the acoustic and optical thicknesses, measured at the end of the process, are comparable to those observed by employing conventional fabrication methods (e.g., vesicle fusion). As shown by QCM-D measurements, the obtained planar bilayers are highly resistant to protein adsorption, and several, but not all, water-miscible organic solvents could be successfully used in the SALB procedure, with isopropanol yielding particularly high-quality bilayers. In addition, fluorescence recovery after photobleaching (FRAP) measurements demonstrated that the coefficient of lateral lipid diffusion in the fabricated bilayers corresponds to that measured earlier in the planar bilayers formed by vesicle fusion. With increasing rate of solvent exchange, it was also observed that the bilayer became incomplete and a phenomenological model was developed in order to explain this feature. The results obtained allowed us to clarify and discriminate likely steps of the SALB formation process as well as determine the corresponding influence of organic solvent type and flow conditions on these steps. Taken together, the findings demonstrate that the SALB formation method can be adapted to a continuous solvent-exchange procedure that is technically minimal, quick, and efficient to form planar bilayers on solid supports.

Structure of Carbon Nanotube Porins in Lipid Bilayers: An in Situ Small-Angle X-ray Scattering (SAXS) Study [Atomic-level structure of carbon nanotube porins in lipid bilayers: an in-situ small-angle x-ray scattering (SAXS) study

DOE PAGES

Tran, Ich C.; Tunuguntla, Ramya H.; Kim, Kyunghoon; ...

2016-06-20

Carbon nanotube porins (CNTPs), small segments of carbon nanotubes capable of forming defined pores in lipid membranes, are important future components for bionanoelectronic devices as they could provide a robust analog of biological membrane channels. Furthermore, in order to control the incorporation of these CNT channels into lipid bilayers, it is important to understand the structure of the CNTPs before and after insertion into the lipid bilayer as well as the impact of such insertion on the bilayer structure. Here we employed a noninvasive in situ probe, small-angle X-ray scattering, to study the integration of CNT porins into dioleoylphosphatidylcholine bilayers.more » These results show that CNTPs in solution are stabilized by a monolayer of lipid molecules wrapped around their outer surface. We also demonstrate that insertion of CNTPs into the lipid bilayer results in decreased bilayer thickness with the magnitude of this effect increasing with the concentration of CNTPs.« less

Large-scale uniform bilayer graphene prepared by vacuum graphitization of 6H-SiC(0001) substrates

NASA Astrophysics Data System (ADS)

Wang, Qingyan; Zhang, Wenhao; Wang, Lili; He, Ke; Ma, Xucun; Xue, Qikun

2013-03-01

We report on the preparation of large-scale uniform bilayer graphenes on nominally flat Si-polar 6H-SiC(0001) substrates by flash annealing in ultrahigh vacuum. The resulting graphenes have a single thickness of one bilayer and consist of regular terraces separated by the triple SiC bilayer steps on the 6H-SiC(0001) substrates. In situ scanning tunneling microscopy reveals that suppression of pit formation on terraces and uniformity of SiC decomposition at step edges are the key factors to the uniform thickness. By studying the surface morphologies prepared under different annealing rates, it is found that the annealing rate is directly related to SiC decomposition, diffusion of the released Si/C atoms and strain relaxation, which together determine the final step structure and density of defects.

Large-scale uniform bilayer graphene prepared by vacuum graphitization of 6H-SiC(0001) substrates.

PubMed

Wang, Qingyan; Zhang, Wenhao; Wang, Lili; He, Ke; Ma, Xucun; Xue, Qikun

2013-03-06

We report on the preparation of large-scale uniform bilayer graphenes on nominally flat Si-polar 6H-SiC(0001) substrates by flash annealing in ultrahigh vacuum. The resulting graphenes have a single thickness of one bilayer and consist of regular terraces separated by the triple SiC bilayer steps on the 6H-SiC(0001) substrates. In situ scanning tunneling microscopy reveals that suppression of pit formation on terraces and uniformity of SiC decomposition at step edges are the key factors to the uniform thickness. By studying the surface morphologies prepared under different annealing rates, it is found that the annealing rate is directly related to SiC decomposition, diffusion of the released Si/C atoms and strain relaxation, which together determine the final step structure and density of defects.

Commensurability condition and hierarchy of fillings for FQHE in higher Landau levels in conventional 2DEG systems and in graphene—monolayer and bilayer

NASA Astrophysics Data System (ADS)

Jacak, Janusz; Jacak, Lucjan

2016-01-01

The structure of the filling rate hierarchy referred to as the fractional quantum Hall effect is studied in higher Landau levels using the commensurability condition. The hierarchy of fillings that are derived in this manner is consistent with the experimental observations of the first three Landau levels in conventional semiconductor Hall systems. The relative poverty of the fractional structure in higher Landau levels compared with the lowest Landau level is explained using commensurability topological arguments. The commensurability criterion for correlated states for higher Landau levels (with n≥slant 1) including the paired states at half fillings of the spin-subbands of these levels is formulated. The commensurability condition is applied to determine the hierarchy of the fractional fillings of Landau levels in the monolayer and bilayer graphene. Good agreement with current experimental observations of fractional quantum Hall effect in the graphene monolayer and bilayer is achieved. The presence of even denominator rates in the hierarchy for fractional quantum Hall effect in the bilayer graphene is also explained.

Neutron Diffraction Studies of Fluid Bilayers with Transmembrane Proteins: Structural Consequences of the Achondroplasia Mutation

PubMed Central

Han, Xue; Mihailescu, Mihaela; Hristova, Kalina

2006-01-01

Achondroplasia, the most common form of human dwarfism, is due to a G380R mutation in the transmembrane domain of fibroblast growth factor receptor 3 (FGFR3) in >97% of the studied cases. While the molecular mechanism of pathology induction is under debate, the structural consequences of the mutation have not been studied. Here we use neutron diffraction to determine the disposition of FGFR3 transmembrane domain in fluid lipid bilayers, and investigate whether the G380R mutation affects the topology of the protein in the bilayer. Our results demonstrate that, in a model system, the G380R mutation induces a shift in the segment that is embedded in the membrane. The center of the hydrocarbon core-embedded segment in the mutant is close to the midpoint between R380 and R397, supporting previous measurements of arginine insertion energetics into the endoplasmic reticulum. The presented results further our knowledge about basic amino-acid insertion into bilayers, and may lead to new insights into the mechanism of pathogenesis in achondroplasia. PMID:16950849

Interaction of Aspirin (Acetylsalicylic Acid) with Lipid Membranes

PubMed Central

Barrett, Matthew A.; Zheng, Songbo; Roshankar, Golnaz; Alsop, Richard J.; Belanger, Randy K. R.; Huynh, Chris; Kučerka, Norbert; Rheinstädter, Maikel C.

2012-01-01

We studied the interaction of Aspirin (acetylsalicylic acid) with lipid membranes using x-ray diffraction for bilayers containing up to 50 mol% of aspirin. From 2D x-ray intensity maps that cover large areas of reciprocal space we determined the position of the ASA molecules in the phospholipid bilayers and the molecular arrangement of the molecules in the plane of the membranes. We present direct experimental evidence that ASA molecules participate in saturated lipid bilayers of DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) and preferably reside in the head group region of the membrane. Up to 50 mol% ASA molecules can be dissolved in this type of bilayer before the lateral membrane organization is disturbed and the membranes are found to form an ordered, 2D crystal-like structure. Furthermore, ASA and cholesterol were found to co-exist in saturated lipid bilayers, with the ASA molecules residing in the head group region and the cholesterol molecules participating in the hydrophobic membrane core. PMID:22529913

Maximally asymmetric transbilayer distribution of anionic lipids alters the structure and interaction with lipids of an amyloidogenic protein dimer bound to the membrane surface

PubMed Central

Cheng, Sara Y.; Chou, George; Buie, Creighton; Vaughn, Mark W.; Compton, Campbell; Cheng, Kwan H.

2016-01-01

We used molecular dynamics simulations to explore the effects of asymmetric transbilayer distribution of anionic phosphatidylserine (PS) lipids on the structure of a protein on the membrane surface and subsequent protein–lipid interactions. Our simulation systems consisted of an amyloidogenic, beta-sheet rich dimeric protein (D42) absorbed to the phosphatidylcholine (PC) leaflet, or protein-contact PC leaflet, of two membrane systems: a single-component PC bilayer and double PC/PS bilayers. The latter comprised of a stable but asymmetric transbilayer distribution of PS in the presence of counterions, with a 1-component PC leaflet coupled to a 1-component PS leaflet in each bilayer. The maximally asymmetric PC/PS bilayer had a non-zero transmembrane potential (TMP) difference and higher lipid order packing, whereas the symmetric PC bilayer had a zero TMP difference and lower lipid order packing under physiologically relevant conditions. Analysis of the adsorbed protein structures revealed weaker protein binding, more folding in the N-terminal domain, more aggregation of the N- and C-terminal domains and larger tilt angle of D42 on the PC leaflet surface of the PC/PS bilayer versus the PC bilayer. Also, analysis of protein-induced membrane structural disruption revealed more localized bilayer thinning in the PC/PS versus PC bilayer. Although the electric field profile in the non-protein-contact PS leaflet of the PC/PS bilayer differed significantly from that in the non-protein-contact PC leaflet of the PC bilayer, no significant difference in the electric field profile in the protein-contact PC leaflet of either bilayer was evident. We speculate that lipid packing has a larger effect on the surface adsorbed protein structure than the electric field for a maximally asymmetric PC/PS bilayer. Our results support the mechanism that the higher lipid packing in a lipid leaflet promotes stronger protein–protein but weaker protein–lipid interactions for a dimeric protein on membrane surfaces. PMID:26827904

Growth patterns for shape-shifting elastic bilayers.

PubMed

van Rees, Wim M; Vouga, Etienne; Mahadevan, L

2017-10-31

Inspired by the differential-growth-driven morphogenesis of leaves, flowers, and other tissues, there is increasing interest in artificial analogs of these shape-shifting thin sheets made of active materials that respond to environmental stimuli such as heat, light, and humidity. But how can we determine the growth patterns to achieve a given shape from another shape? We solve this geometric inverse problem of determining the growth factors and directions (the metric tensors) for a given isotropic elastic bilayer to grow into a target shape by posing and solving an elastic energy minimization problem. A mathematical equivalence between bilayers and curved monolayers simplifies the inverse problem considerably by providing algebraic expressions for the growth metric tensors in terms of those of the final shape. This approach also allows us to prove that we can grow any target surface from any reference surface using orthotropically growing bilayers. We demonstrate this by numerically simulating the growth of a flat sheet into a face, a cylindrical sheet into a flower, and a flat sheet into a complex canyon-like structure.

Growth patterns for shape-shifting elastic bilayers

PubMed Central

van Rees, Wim M.; Vouga, Etienne; Mahadevan, L.

2017-01-01

Inspired by the differential-growth-driven morphogenesis of leaves, flowers, and other tissues, there is increasing interest in artificial analogs of these shape-shifting thin sheets made of active materials that respond to environmental stimuli such as heat, light, and humidity. But how can we determine the growth patterns to achieve a given shape from another shape? We solve this geometric inverse problem of determining the growth factors and directions (the metric tensors) for a given isotropic elastic bilayer to grow into a target shape by posing and solving an elastic energy minimization problem. A mathematical equivalence between bilayers and curved monolayers simplifies the inverse problem considerably by providing algebraic expressions for the growth metric tensors in terms of those of the final shape. This approach also allows us to prove that we can grow any target surface from any reference surface using orthotropically growing bilayers. We demonstrate this by numerically simulating the growth of a flat sheet into a face, a cylindrical sheet into a flower, and a flat sheet into a complex canyon-like structure. PMID:29078336

Focused-ion-beam induced interfacial intermixing of magnetic bilayers for nanoscale control of magnetic properties.

PubMed

Burn, D M; Hase, T P A; Atkinson, D

2014-06-11

Modification of the magnetic properties in a thin-film ferromagnetic/non-magnetic bilayer system by low-dose focused ion-beam (FIB) induced intermixing is demonstrated. The highly localized capability of FIB may be used to locally control magnetic behaviour at the nanoscale. The magnetic, electronic and structural properties of NiFe/Au bilayers were investigated as a function of the interfacial structure that was actively modified using focused Ga(+) ion irradiation. Experimental work used MOKE, SQUID, XMCD as well as magnetoresistance measurements to determine the magnetic behavior and grazing incidence x-ray reflectivity to elucidate the interfacial structure. Interfacial intermixing, induced by low-dose irradiation, is shown to lead to complex changes in the magnetic behavior that are associated with monotonic structural evolution of the interface. This behavior may be explained by changes in the local atomic environment within the interface region resulting in a combination of processes including the loss of moment on Ni and Fe, an induced moment on Au and modifications to the spin-orbit coupling between Au and NiFe.

CryoEM structures of membrane pore and prepore complex reveal cytolytic mechanism of Pneumolysin

PubMed Central

van Pee, Katharina; Neuhaus, Alexander; D'Imprima, Edoardo; Mills, Deryck J; Kühlbrandt, Werner; Yildiz, Özkan

2017-01-01

Many pathogenic bacteria produce pore-forming toxins to attack and kill human cells. We have determined the 4.5 Å structure of the ~2.2 MDa pore complex of pneumolysin, the main virulence factor of Streptococcus pneumoniae, by cryoEM. The pneumolysin pore is a 400 Å ring of 42 membrane-inserted monomers. Domain 3 of the soluble toxin refolds into two ~85 Å β-hairpins that traverse the lipid bilayer and assemble into a 168-strand β-barrel. The pore complex is stabilized by salt bridges between β-hairpins of adjacent subunits and an internal α-barrel. The apolar outer barrel surface with large sidechains is immersed in the lipid bilayer, while the inner barrel surface is highly charged. Comparison of the cryoEM pore complex to the prepore structure obtained by electron cryo-tomography and the x-ray structure of the soluble form reveals the detailed mechanisms by which the toxin monomers insert into the lipid bilayer to perforate the target membrane. DOI: http://dx.doi.org/10.7554/eLife.23644.001 PMID:28323617

Acemetacin-phosphatidylcholine interactions are determined by the drug ionization state.

PubMed

Pereira-Leite, Catarina; Nunes, Cláudia; Grahl, Débora; Bozelli, José C; Schreier, Shirley; Kamma-Lorger, Christina S; Cuccovia, Iolanda M; Reis, Salette

2018-05-17

Gastrointestinal (GI) toxicity is a major drawback of the chronic use of nonsteroidal anti-inflammatory drugs (NSAIDs). The NSAIDs topical actions on the protective phospholipid layers of the GI mucosa seem to be a central toxicity mechanism of these pharmaceuticals. This work describes the interactions of acemetacin, a commercialized NSAID, with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) bilayers at pH 3.0, 5.0, and 7.4. This pH range was chosen to mimic the pH gradient found in the gastric mucosa, and to ultimately gain insights into the mechanisms underlying the acemetacin-induced gastric toxicity. Various experimental techniques were combined to characterize the partitioning of acemetacin in DMPC bilayers, and its effects on the phase transition behavior, as well as the structure and dynamics of DMPC bilayers. The acemetacin-DMPC interactions were clearly pH-dependent. The neutral (protonated) form of acemetacin had more affinity for the DMPC bilayer than the negatively charged form. Due to the higher affinity of neutral acemetacin, the drug effects on the phase transition and the structure and dynamics of the DMPC bilayer were more pronounced at lower pH values. In general, acemetacin decreased the temperature and the cooperativity of the lipid phase transition and induced changes in the packing and dynamics of the DMPC bilayer. These results support the hypothesis that acemetacin-induced gastric toxicity may be related to its effects on the protective phospholipid layers of the mucosal barrier.

Magnetic properties of magnetic bilayer Kekulene structure: A Monte Carlo study

NASA Astrophysics Data System (ADS)

Jabar, A.; Masrour, R.

2018-06-01

In the present work, we have studied the magnetic properties of magnetic bilayer Kekulene structure with mixed spin-5/2 and spin-2 Ising model using Monte Carlo study. The magnetic phase diagrams of mixed spins Ising model have been given. The thermal total, partial magnetization and magnetic susceptibilities of the mixed spin-5/2 and spin-2 Ising model on a magnetic bilayer Kekulene structure are obtained. The transition temperature has been deduced. The effect of crystal field and exchange interactions on the this bilayers has been studied. The partial and total magnetic hysteresis cycles of the mixed spin-5/2 and spin-2 Ising model on a magnetic bilayer Kekulene structure have been given. The superparamagnetism behavior is observed in magnetic bilayer Kekulene structure. The magnetic coercive field decreases with increasing the exchange interactions between σ-σ and temperatures values and increases with increasing the absolute value of exchange interactions between σ-S. The multiple hysteresis behavior appears.

Profile structures of the voltage-sensor domain and the voltage-gated K+-channel vectorially oriented in a single phospholipid bilayer membrane at the solid-vapor and solid-liquid interfaces determined by x-ray interferometry

PubMed Central

Gupta, S.; Liu, J.; Strzalka, J.; Blasie, J. K.

2011-01-01

One subunit of the prokaryotic voltage-gated potassium ion channel from Aeropyrum pernix (KvAP) is comprised of six transmembrane α helices, of which S1–S4 form the voltage-sensor domain (VSD) and S5 and S6 contribute to the pore domain (PD) of the functional homotetramer. However, the mechanism of electromechanical coupling interconverting the closed-to-open (i.e., nonconducting-to-K+-conducting) states remains undetermined. Here, we have vectorially oriented the detergent (OG)-solubilized VSD in single monolayers by two independent approaches, namely “directed-assembly” and “self-assembly,” to achieve a high in-plane density. Both utilize Ni coordination chemistry to tether the protein to an alkylated inorganic surface via its C-terminal His6 tag. Subsequently, the detergent is replaced by phospholipid (POPC) via exchange, intended to reconstitute a phospholipid bilayer environment for the protein. X-ray interferometry, in which interference with a multilayer reference structure is used to both enhance and phase the specular x-ray reflectivity from the tethered single membrane, was used to determine directly the electron density profile structures of the VSD protein solvated by detergent versus phospholipid, and with either a moist He (moderate hydration) or bulk aqueous buffer (high hydration) environment to preserve a native structure conformation. Difference electron density profiles, with respect to the multilayer substrate itself, for the VSD-OG monolayer and VSD-POPC membranes at both the solid-vapor and solid-liquid interfaces, reveal the profile structures of the VSD protein dominating these profiles and further indicate a successful reconstitution of a lipid bilayer environment. The self-assembly approach was similarly extended to the intact full-length KvAP channel for comparison. The spatial extent and asymmetry in the profile structures of both proteins confirm their unidirectional vectorial orientation within the reconstituted membrane and indicate retention of the protein’s folded three-dimensional tertiary structure upon completion of membrane bilayer reconstitution. Moreover, the resulting high in-plane density of vectorially oriented protein within a fully hydrated single phospholipid bilayer membrane at the solid-liquid interface will enable investigation of their conformational states as a function of the transmembrane electric potential. PMID:22060407

Artificial multiferroic structures using soft magnetostrictive bilayers on Pb(Mg1/3Nb2/3)-PbTiO3

NASA Astrophysics Data System (ADS)

Miskevich, E.; Alshammari, F. K.; Yang, W.-G.; Sharp, J.; Baco, S.; Leong, Z.; Abbas, Q. A.; Morley, N. A.

2018-02-01

Artificial multiferroic structures are of great interest as they combine two or more functionalities together. One example of these structures is magnetostrictive films grown on top of piezoelectric substrates; allowing the magnetisation hysteresis loop of the magnetostrictive film to be manipulated using an electric field across the structure rather than a magnetic field. In this paper, we have studied the multiferroic structure NiFe/FeCo/Ti/Pb(Mg1/3Nb2/3)-PbTiO3 (PMN-PT) as a function of the electric and magnetic field. Soft magnetostrictive bilayer films (NiFe/FeCo) are studied, as often applications require soft magnetic properties (small coercive and anisotropy fields) combined with larger magnetostrictive constants. Unfortunately, FeCo films can have coercive fields that are too large, while NiFe films’ magnetostriction constants are almost zero; thus, combining the two together should produce the ‘ideal’ soft magnetostrictive film. It was found that the addition of a thin NiFe film onto the FeCo film reduced the coercive field and remnant magnetisation on the application of an applied voltage in comparison to just the FeCo film. It was also determined that for the NiFe/FeCo bilayer the magnetisation switchability was ~100% on the application of 8 kV cm-m, which was higher than the monolayer FeCo films at the same applied field, demonstrating improvement of the multiferroic behaviour by the soft magnetic/magnetostrictive bilayer.

A systematic investigation and insight into the formation mechanism of bilayers of fatty acid/soap mixtures in aqueous solutions.

PubMed

Xu, Wenlong; Song, Aixin; Dong, Shuli; Chen, Jingfei; Hao, Jingcheng

2013-10-08

Vesicles are the most common form of bilayer structures in fatty acid/soap mixtures in aqueous solutions; however, a peculiar bilayer structure called a "planar sheet" was found for the first time in the mixtures. In the past few decades, considerable research has focused on the formation theory of bilayers in fatty acid/soap mixtures. The hydrogen bond theory has been widely accepted by scientists to explain the formation of bilayers. However, except for the hydrogen bond, no other driving forces were proposed systematically. In this work, three kinds of weak interactions were investigated in detail, which could perfectly demonstrate the formation mechanism of bilayer structures in the fatty acid/soap mixtures in aqueous solutions. (i) The influence of hydrophobic interaction was detected by changing the chain length of fatty acid (C(n)H(2n+1)COOH), in which n = 10 to 18, the phase behavior was investigated, and the phase region was presented. With the help of cryogenic transmission electron microscopy (cryo-TEM) observations, deuterium nuclear magnetic resonance ((2)H NMR), and X-ray diffraction (XRD) measurements, the vesicles and planar sheets were determined. The chain length of C(n)H(2n+1)COOH has an important effect on the physical state of the hydrophobic chain, resulting in an obvious difference in the viscoelasticity of the solution samples. (ii) The existence of hydrogen bonds between fatty acids and their soaps in aqueous solutions was demonstrated by Fourier transform infrared (FT-IR) spectroscopy and molecule dynamical simulation. From the pH measurements, the pH ranges of the bilayer formation were at the pKa values of fatty acids, respectively. (iii) Counterions can be embedded in the stern layer of the bilayers and screen the electrostatic repulsion between the COO(-) anionic headgroups. FT-IR characterization demonstrated a bidentate bridging coordination mode between counterions and carboxylates. The conductivity measurements provided the degree of counterion binding (β = 0.854), indicating the importance of the counterions.

Self-assembled PCBM bilayers on graphene and HOPG examined by AFM and STM

NASA Astrophysics Data System (ADS)

Li, Yanlong; Chen, Chuanhui; Burton, John; Park, Kyungwha; Heflin, James R.; Tao, Chenggang

2018-05-01

In this work we report fabrication and characterization of phenyl-C61-butyric acid methyl ester (PCBM) bilayer structures on graphene and highly oriented pyrolytic graphite (HOPG). Through careful control of the PCBM solution concentration (from 0.1 to 2 mg ml-1) and the deposition conditions, we demonstrate that PCBM molecules self-assemble into bilayer structures on graphene and HOPG substrates. Interestingly, the PCBM bilayers are formed with two distinct heights on HOPG, but only one unique representative height on graphene. At elevated annealing temperatures, edge diffusion allows neighboring vacancies to merge into a more ordered structure. This is, to the best of our knowledge, the first experimental realization of PCBM bilayer structures on graphene. This work could provide valuable insight into fabrication of new hybrid, ordered structures for applications to organic solar cells.

Self-assembled PCBM bilayers on graphene and HOPG examined by AFM and STM.

PubMed

Li, Yanlong; Chen, Chuanhui; Burton, John; Park, Kyungwha; Heflin, James R; Tao, Chenggang

2018-05-04

In this work we report fabrication and characterization of phenyl-C61-butyric acid methyl ester (PCBM) bilayer structures on graphene and highly oriented pyrolytic graphite (HOPG). Through careful control of the PCBM solution concentration (from 0.1 to 2 mg ml -1 ) and the deposition conditions, we demonstrate that PCBM molecules self-assemble into bilayer structures on graphene and HOPG substrates. Interestingly, the PCBM bilayers are formed with two distinct heights on HOPG, but only one unique representative height on graphene. At elevated annealing temperatures, edge diffusion allows neighboring vacancies to merge into a more ordered structure. This is, to the best of our knowledge, the first experimental realization of PCBM bilayer structures on graphene. This work could provide valuable insight into fabrication of new hybrid, ordered structures for applications to organic solar cells.

Adsorption configurations and scanning voltage determined STM images of small hydrogen clusters on bilayer graphene.

PubMed

Cao, Teng Fei; Huang, Liang Feng; Zheng, Xiao Hong; Zhou, Wang Huai; Zeng, Zhi

2013-11-21

By density functional theory calculations, the scanning tunneling microscopy (STM) images of various hydrogen clusters adsorbed on bilayer-graphene are systematically simulated. The hydrogen configurations of the STM images observed in the experiments have been thoroughly figured out. In particular, two kinds of hydrogen dimers (ortho-dimer, para-dimer) and two kinds of tetramers (tetramer-A, -B) are determined to be the hydrogen configurations corresponding to the ellipsoidal-like STM images with different structures and sizes. One particular hexamer (hexamer-B) is the hydrogen configuration generating the star-like STM images. For each hydrogen cluster, the simulated STM images show unique voltage-dependent features, which provides a feasible way to determine hydrogen adsorption states on graphene or graphite surface in the experiments by varying-voltage measurements. Stability analysis proves that the above determined hydrogen configurations are quite stable on graphene, hence they are likely to be detected in the STM experiments. Consequently, through systematic analysis of the STM images and the stability of hydrogen clusters on bilayer graphene, many experimental observations have been consistently explained.

Probing topology and dynamics of the second transmembrane domain (M2δ) of the acetyl choline receptor using magnetically aligned lipid bilayers (bicelles) and EPR spectroscopy.

PubMed

Sahu, Indra D; Mayo, Daniel J; Subbaraman, Nidhi; Inbaraj, Johnson J; McCarrick, Robert M; Lorigan, Gary A

2017-08-01

Characterizing membrane protein structure and dynamics in the lipid bilayer membrane is very important but experimentally challenging. EPR spectroscopy offers a unique set of techniques to investigate a membrane protein structure, dynamics, topology, and distance constraints in lipid bilayers. Previously our lab demonstrated the use of magnetically aligned phospholipid bilayers (bicelles) for probing topology and dynamics of the membrane peptide M2δ of the acetyl choline receptor (AchR) as a proof of concept. In this study, magnetically aligned phospholipid bilayers and rigid spin labels were further utilized to provide improved dynamic information and topology of M2δ peptide. Seven TOAC-labeled AchR M2δ peptides were synthesized to demonstrate the utility of a multi-labeling amino acid substitution alignment strategy. Our data revealed the helical tilts to be 11°, 17°, 9°, 17°, 16°, 11°, 9°±4° for residues I7TOAC, Q13TOAC, A14TOAC, V15TOAC, C16TOAC, L17TOAC, and L18TOAC, respectively. The average helical tilt of the M2δ peptide was determined to be ∼13°. This study also revealed that the TOAC labels were attached to the M2δ peptide with different dynamics suggesting that the sites towards the C-terminal end are more rigid when compared to the sites towards the N-terminus. The dynamics of the TOAC labeled sites were more resolved in the aligned samples when compared to the randomly disordered samples. This study highlights the use of magnetically aligned lipid bilayer EPR technique to determine a more accurate helical tilt and more resolved local dynamics of AchR M2δ peptide. Copyright © 2017 Elsevier B.V. All rights reserved.

Improved electrical performance and bias stability of solution-processed active bilayer structure of indium zinc oxide based TFT.

PubMed

Seo, Jin-Suk; Bae, Byeong-Soo

2014-09-10

We fabricated active single- and bilayer structure thin film transistors (TFTs) with aluminum or gallium doped (IZO:Al or IZO:Ga) and undoped indium zinc oxide (IZO) thin film layers using an aqueous solution process. The electrical performance and bias stability of these active single- and bilayer structure TFTs were investigated and compared to reveal the effects of Al/Gal doping and bilayer structure. The single-layer structure IZO TFT shows a high mobility of 19 cm(2)/V · s with a poor positive bias stability (PBS) of ΔVT + 3.4 V. However, Al/Ga doped in IZO TFT reduced mobility to 8.5-9.9 cm(2)/V · s but improved PBS to ΔVT + 1.6-1.7 V due to the reduction of oxygen vacancy. Thus, it is found the bilayer structure TFTs with a combination of bottom- and top-layer compositions modify both the mobility and bias stability of the TFTs to be optimized. The bilayer structure TFT with an IZO:X bottom layer possess high mobility and an IZO bottom layer improves the PBS.

Maximally asymmetric transbilayer distribution of anionic lipids alters the structure and interaction with lipids of an amyloidogenic protein dimer bound to the membrane surface.

PubMed

Cheng, Sara Y; Chou, George; Buie, Creighton; Vaughn, Mark W; Compton, Campbell; Cheng, Kwan H

2016-03-01

We used molecular dynamics simulations to explore the effects of asymmetric transbilayer distribution of anionic phosphatidylserine (PS) lipids on the structure of a protein on the membrane surface and subsequent protein-lipid interactions. Our simulation systems consisted of an amyloidogenic, beta-sheet rich dimeric protein (D42) absorbed to the phosphatidylcholine (PC) leaflet, or protein-contact PC leaflet, of two membrane systems: a single-component PC bilayer and double PC/PS bilayers. The latter comprised of a stable but asymmetric transbilayer distribution of PS in the presence of counterions, with a 1-component PC leaflet coupled to a 1-component PS leaflet in each bilayer. The maximally asymmetric PC/PS bilayer had a non-zero transmembrane potential (TMP) difference and higher lipid order packing, whereas the symmetric PC bilayer had a zero TMP difference and lower lipid order packing under physiologically relevant conditions. Analysis of the adsorbed protein structures revealed weaker protein binding, more folding in the N-terminal domain, more aggregation of the N- and C-terminal domains and larger tilt angle of D42 on the PC leaflet surface of the PC/PS bilayer versus the PC bilayer. Also, analysis of protein-induced membrane structural disruption revealed more localized bilayer thinning in the PC/PS versus PC bilayer. Although the electric field profile in the non-protein-contact PS leaflet of the PC/PS bilayer differed significantly from that in the non-protein-contact PC leaflet of the PC bilayer, no significant difference in the electric field profile in the protein-contact PC leaflet of either bilayer was evident. We speculate that lipid packing has a larger effect on the surface adsorbed protein structure than the electric field for a maximally asymmetric PC/PS bilayer. Our results support the mechanism that the higher lipid packing in a lipid leaflet promotes stronger protein-protein but weaker protein-lipid interactions for a dimeric protein on membrane surfaces. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

A Two-Tailed Phosphopeptide Crystallizes to Form a Lamellar Structure.

PubMed

Pellach, Michal; Mondal, Sudipta; Harlos, Karl; Mance, Deni; Baldus, Marc; Gazit, Ehud; Shimon, Linda J W

2017-03-13

The crystal structure of a designed phospholipid-inspired amphiphilic phosphopeptide at 0.8 Å resolution is presented. The phosphorylated β-hairpin peptide crystallizes to form a lamellar structure that is stabilized by intra- and intermolecular hydrogen bonding, including an extended β-sheet structure, as well as aromatic interactions. This first reported crystal structure of a two-tailed peptidic bilayer reveals similarities in thickness to a typical phospholipid bilayer. However, water molecules interact with the phosphopeptide in the hydrophilic region of the lattice. Additionally, solid-state NMR was used to demonstrate correlation between the crystal structure and supramolecular nanostructures. The phosphopeptide was shown to self-assemble into semi-elliptical nanosheets, and solid-state NMR provides insight into the self-assembly mechanisms. This work brings a new dimension to the structural study of biomimetic amphiphilic peptides with determination of molecular organization at the atomic level. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessment of pseudo-bilayer structures in the heterogate germanium electron-hole bilayer tunnel field-effect transistor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Padilla, J. L., E-mail: jose.padilladelatorre@epfl.ch; Alper, C.; Ionescu, A. M.

2015-06-29

We investigate the effect of pseudo-bilayer configurations at low operating voltages (≤0.5 V) in the heterogate germanium electron-hole bilayer tunnel field-effect transistor (HG-EHBTFET) compared to the traditional bilayer structures of EHBTFETs arising from semiclassical simulations where the inversion layers for electrons and holes featured very symmetric profiles with similar concentration levels at the ON-state. Pseudo-bilayer layouts are attained by inducing a certain asymmetry between the top and the bottom gates so that even though the hole inversion layer is formed at the bottom of the channel, the top gate voltage remains below the required value to trigger the formation of themore » inversion layer for electrons. Resulting benefits from this setup are improved electrostatic control on the channel, enhanced gate-to-gate efficiency, and higher I{sub ON} levels. Furthermore, pseudo-bilayer configurations alleviate the difficulties derived from confining very high opposite carrier concentrations in very thin structures.« less

Coherent assembly of heterostructures in ternary and quaternary carbonitrides

NASA Astrophysics Data System (ADS)

Caicedo, J. C.; Aperador, W.; Saldarriaga, W.

2018-05-01

In this study, ternary and quaternary carbonitride heterostructure systems were grown on silicon (100) substrates in order to investigate coherent assembly in TiCN/TiNbCN. The heterostructure films were grown using the reactive r. f. magnetron sputtering technique by systematically varying the bilayer period (Λ) and the bilayer number (n), while maintaining a constant total coating thickness (∼3 μm). The heterostructures were characterized by high angle X-ray diffraction (HA-XRD) and low angle X-ray diffraction, while the TiCN and TiNbCN layers were analyzed by X-ray photoelectron spectroscopy and transmission electron microscopy. The HA-XRD results indicated preferential growth in the face-centered cubic (111) crystal structure for the [TiCN/TiNbCN]n heterostructures. The maximum coherent assembly was observed with the presence of satellite peaks. Thus, ternary and quaternary carbonitride films were designed and deposited on Si (100) substrates with bilayer periods (Λ) in a broad range from nanometers to hundreds of nanometers in order to study the structural evolution and coherent assembly progress as the bilayer thickness decreased. We determined physical properties comprising the critical angle (θc) (0.362°), electronic density (ρe) (0.521 × 1033 el/m3), dispersion coefficient (δ) (0.554 el/m3), and refractive index (n) (0.999944) as functions of the number of bilayers (n).

Current-driven second-harmonic domain wall resonance in ferromagnetic metal/nonmagnetic metal bilayers: A field-free method for spin Hall angle measurements

NASA Astrophysics Data System (ADS)

Hajiali, M. R.; Hamdi, M.; Roozmeh, S. E.; Mohseni, S. M.

2017-10-01

We study the ac current-driven domain wall motion in bilayer ferromagnetic metal (FM)/nonmagnetic metal (NM) nanowires. The solution of the modified Landau-Lifshitz-Gilbert equation including all the spin transfer torques is used to describe motion of the domain wall in the presence of the spin Hall effect. We show that the domain wall center has a second-harmonic frequency response in addition to the known first-harmonic excitation. In contrast to the experimentally observed second-harmonic response in harmonic Hall measurements of spin-orbit torque in magnetic thin films, this second-harmonic response directly originates from spin-orbit torque driven domain wall dynamics. Based on the spin current generated by domain wall dynamics, the longitudinal spin motive force generated voltage across the length of the nanowire is determined. The second-harmonic response introduces additionally a practical field-free and all-electrical method to probe the effective spin Hall angle for FM/NM bilayer structures that could be applied in experiments. Our results also demonstrate the capability of utilizing FM/NM bilayer structures in domain wall based spin-torque signal generators and resonators.

Determination of Structural Topology of a Membrane Protein in Lipid -Bilayers using Polarization Optimized Experiments (POE) for Static and MAS Solid State NMR Spectroscopy

PubMed Central

Mote, Kaustubh R.; Gopinath, T.; Veglia, Gianluigi

2013-01-01

The low sensitivity inherent to both the static and magic angle spinning techniques of solid-state NMR (ssNMR) spectroscopy has thus far limited the routine application of multidimensional experiments to determine the structure of membrane proteins in lipid bilayers. Here, we demonstrate the advantage of using a recently developed class of experiments, polarization optimized experiments (POE), for both static and MAS spectroscopy to achieve higher sensitivity and substantial time-savings for 2D and 3D experiments. We used sarcolipin, a single pass membrane protein, reconstituted in oriented bicelles (for oriented ssNMR) and multilamellar vesicles (for MAS ssNMR) as a benchmark. The restraints derived by these experiments are then combined into a hybrid energy function to allow simultaneous determination of structure and topology. The resulting structural ensemble converged to a helical conformation with a backbone RMSD ∼ 0.44 Å, a tilt angle of 24° ± 1°, and an azimuthal angle of 55° ± 6°. This work represents a crucial first step toward obtaining high-resolution structures of large membrane proteins using combined multidimensional O-ssNMR and MAS-ssNMR. PMID:23963722

Electronic compressibility of bilayer graphene

NASA Astrophysics Data System (ADS)

Henriksen, Erik

2011-03-01

We have recently measured the electronic compressibility of bilayer graphene, allowing exploration of the thermodynamic density of states as a function of applied electric and magnetic fields. Utilizing dual-gated field-effect devices, we can independently vary both the carrier density and the size of the tunable band gap. An oscillating voltage applied to a back gate generates corresponding signals in the top gate via electric fields lines which penetrate the graphene, thereby allowing a direct measurement of the inverse compressibility, K-1 , of the bilayer. We have mapped K-1 , which is proportional to the inverse density of states, as a function of the top and back gate voltages in zero and finite magnetic field. A sharp increase in K-1 near zero density is observed with increasing electric field strength, signaling the controlled opening of a band gap. At high magnetic fields, broad Landau level (LL) oscillations are observed, directly revealing the doubled degeneracy of the lowest LL and allowing for a determination of the disorder broadening of the levels. We compare our results to tight-binding calculations of the bilayer band structure, and to recent theoretical studies of the compressibility of bilayer graphene. Together, these clearly illustrate the unusual hyperbolic nature of the low energy band structure, reveal a sizeable electron-hole asymmetry, and suggest that many-body interactions play only a small role in bilayer-on-substrate devices. This work is a collaboration with J. P. Eisenstein of Caltech, and is supported by the NSF under Grant No. DMR-0552270 and the DOE under Grant No. DE-FG03-99ER45766.

Effects of cholesterol concentration on the interaction of cytarabine with lipid membranes: a molecular dynamics simulation study.

PubMed

Karami, Leila; Jalili, Seifollah

2015-01-01

Liposomal cytarabine, DepoCyt, is a chemotherapy agent which is used in cancer treatment. This form of cytarabine has more efficacy and fewer side effects relative to the other forms. Since DepoCyt contains the cytarabine encapsulated within phosphatidylcholine and the sterol molecules, we modeled dioleoylphosphatidylcholine (DOPC)/cholesterol bilayer membrane as a carrier for cytarabine to study drug-bilayer interactions. For this purpose, we performed a series of united-atom molecular dynamics (MD) simulations for 25 ns to investigate the interactions between cytarabine and cholesterol-containing DOPC lipid bilayers. Only the uncharged form of cytarabine molecule was investigated. In this study, different levels of the cholesterol content (0, 20, and 40%) were used. MD simulations allowed us to determine dynamical and structural properties of the bilayer membrane and to estimate the preferred location and orientation of the cytarabine molecule inside the bilayer membrane. Properties such as membrane thickness, area per lipid, diffusion coefficient, mass density, bilayer packing, order parameters, and intermolecular interactions were examined. The results show that by increasing the cholesterol concentration in the lipid bilayers, the bilayer thickness increases and area per lipid decreases. Moreover, in accordance with the experiments, our calculations show that cholesterol molecules have ordering effect on the hydrocarbon acyl chains. Furthermore, the cytarabine molecule preferentially occupies the polar region of the lipid head groups to form specific interactions (hydrogen bonds). Our results fully support the experimental data. Our finding about drug-bilayer interaction is crucial for the liposomal drug design.

Temperature-driven evolution of critical points, interlayer coupling, and layer polarization in bilayer Mo S2

NASA Astrophysics Data System (ADS)

Du, Luojun; Zhang, Tingting; Liao, Mengzhou; Liu, Guibin; Wang, Shuopei; He, Rui; Ye, Zhipeng; Yu, Hua; Yang, Rong; Shi, Dongxia; Yao, Yugui; Zhang, Guangyu

2018-04-01

The recently emerging two-dimensional (2D) transition-metal dichalcogenides (TMDCs) have been a fertile ground for exploring abundant exotic physical properties. Critical points, the extrema or saddle points of electronic bands, are the cornerstone of condensed-matter physics and fundamentally determine the optical and transport phenomena of the TMDCs. However, for bilayer Mo S2 , a typical TMDC and the unprecedented electrically tunable venue for valleytronics, there has been a considerable controversy on its intrinsic electronic structure, especially for the conduction band-edge locations. Moreover, interlayer hopping and layer polarization in bilayer Mo S2 which play vital roles in valley-spintronic applications have remained experimentally elusive. Here, we report the experimental observation of intrinsic critical points locations, interlayer hopping, layer-spin polarization, and their evolution with temperature in bilayer Mo S2 by performing temperature-dependent photoluminescence. Our measurements confirm that the conduction-band minimum locates at the Kc instead of Qc, and the energy splitting between Qc and Kc redshifts with a descent of temperature. Furthermore, the interlayer hopping energy for holes and temperature-dependent layer polarization are quantitatively determined. Our observations are in good harmony with density-functional theory calculations.

Double Barriers and Magnetic Field in Bilayer Graphene

NASA Astrophysics Data System (ADS)

Redouani, Ilham; Jellal, Ahmed; Bahlouli, Hocine

2015-12-01

We study the transmission probability in an AB-stacked bilayer graphene of Dirac fermions scattered by a double-barrier structure in the presence of a magnetic field. We take into account the full four bands structure of the energy spectrum and use the suitable boundary conditions to determine the transmission probability. Our numerical results show that for energies higher than the interlayer coupling, four ways for transmission are possible while for energies less than the height of the barrier, Dirac fermions exhibit transmission resonances and only one transmission channel is available. We show that, for AB-stacked bilayer graphene, there is no Klein tunneling at normal incidence. We find that the transmission displays sharp peaks inside the transmission gap around the Dirac point within the barrier regions while they are absent around the Dirac point in the well region. The effect of the magnetic field, interlayer electrostatic potential, and various barrier geometry parameters on the transmission probabilities is also discussed.

Aspirin Increases the Solubility of Cholesterol in Lipid Membranes

NASA Astrophysics Data System (ADS)

Alsop, Richard; Barrett, Matthew; Zheng, Sonbo; Dies, Hannah; Rheinstadter, Maikel

2014-03-01

Aspirin (ASA) is often prescribed for patients with high levels of cholesterol for the secondary prevention of myocardial events, a regimen known as the Low-Dose Aspirin Therapy. We have recently shown that Aspirin partitions in lipid bilayers. However, a direct interplay between ASA and cholesterol has not been investigated. Cholesterol is known to insert itself into the membrane in a dispersed state at moderate concentrations (under ~37.5%) and decrease fluidity of membranes. We prepared model lipid membranes containing varying amounts of both ASA and cholesterol molecules. The structure of the bilayers as a function of ASA and cholesterol concentration was determined using high-resolution X-ray diffraction. At cholesterol levels of more than 40mol%, immiscible cholesterol plaques formed. Adding ASA to the membranes was found to dissolve the cholesterol plaques, leading to a fluid lipid bilayer structure. We present first direct evidence for an interaction between ASA and cholesterol on the level of the cell membrane.

Molecular dynamics simulation of sodium dodecylsulfate (SDS) bilayers.

PubMed

Zhang, Hongshu; Yuan, Shiling; Sun, Jichao; Liu, Jianqiang; Li, Haiping; Du, Na; Hou, Wanguo

2017-11-15

Sodium dodecylsulfate (SDS) - a simple single tailed surfactant (STS) can form stable vesicles from its micellar solution without any additives under the mediation of solid surfaces. To further understand the mechanism of this transition on the molecular level, molecular dynamics simulations are performed to study segments of SDS bilayers (as part of vesicles) in the bulk solution systematically, at the moment that the lower leaflet of bilayers already detached from solid surfaces. The SDS membrane would rather keep their bilayers structure than return to micelles when the initial interdigitated degree (δ i ) between alkyl chains is more than 8.0±1.4%. And the interdigitated degree is always approaching to 31.7±2.0% while the equilibrium is reached. The aggregates behave as curved bilayers, planar bilayers, perforated bilayers, and micelles with the increase of the lower leaflet cross-sectional area. Besides, the structures of salt bridge and water bridge structures are formed between DS - and Na + ions or water molecules, which contribute to the stability of SDS bilayers. The distribution difference of the salt bridges along the direction of S-O axis between the two leaflets leads to the asymmetry of the bilayers, which plays supplementary role to the formation of bilayers curvature. We expect that this work help to shed light on the understanding of interface phenomena and the mechanism of simple single-tailed surfactant vesicle self-assembly on the molecular level. Copyright © 2017 Elsevier Inc. All rights reserved.

Voltage-Gated Channel Mechanosensitivity: Fact or Friction?

PubMed Central

Morris, Catherine E.

2011-01-01

The heart is a continually active pulsatile fluid pump. It generates appropriate forces by precisely timed and spaced engagement of its contractile machinery. Largely, it makes its own control signals, the most crucial of which are precisely timed and spaced fluxes of ions across the sarcolemma, achieved by the timely opening and closing of diverse voltage-gated channels (VGC). VGCs have four voltage sensors around a central ion-selective pore that opens and closes under the influence of membrane voltage. Operation of any VGC is secondarily tuned by the mechanical state (i.e., structure) of the bilayer in which it is embedded. Rates of opening and closing, in other words, vary with bilayer structure. Thus, in the intensely mechanical environment of the myocardium and its vasculature, VGCs kinetics might be routinely modulated by reversible and irreversible nano-scale changes in bilayer structure. If subtle bilayer deformations are routine in the pumping heart, VGCs could be subtly transducing bilayer mechanical signals, thereby tuning cardiac rhythmicity, collectively contributing to mechano-electric feedback. Reversible bilayer deformations would be expected with changing shear flows and tissue distension, while irreversible bilayer restructuring occurs with ischemia, inflammation, membrane remodeling, etc. I suggest that tools now available could be deployed to help probe whether/how the inherent mechanosensitivity of VGCs – an attribute substantially reflecting the dependence of voltage sensor stability on bilayer structure – contributes to cardiac rhythmicity. Chief among these tools are voltage sensor toxins (whose inhibitory efficacy varies with the mechanical state of bilayer) and arrhythmia-inducing VGC mutants with distinctive mechano-phenotypes. PMID:21660289

The anomalously high melting temperature of bilayer ice.

PubMed

Kastelowitz, Noah; Johnston, Jessica C; Molinero, Valeria

2010-03-28

Confinement of water usually depresses its melting temperature. Here we use molecular dynamics simulations to determine the liquid-crystal equilibrium temperature for water confined between parallel hydrophobic or mildly hydrophilic plates as a function of the distance between the surfaces. We find that bilayer ice, an ice polymorph in which the local environment of each water molecule strongly departs from the most stable tetrahedral structure, has the highest melting temperature (T(m)) of the series of l-layer ices. The melting temperature of bilayer ice is not only unusually high compared to the other confined ices, but also above the melting point of bulk hexagonal ice. Recent force microscopy experiments of water confined between graphite and a tungsten tip reveal the formation of ice at room temperature [K. B. Jinesh and J. W. M. Frenken, Phys. Rev. Lett. 101, 036101 (2008)]. Our results suggest that bilayer ice, for which we compute a T(m) as high as 310 K in hydrophobic confinement, is the crystal formed in those experiments.

Interlayer couplings, Moiré patterns, and 2D electronic superlattices in MoS2/WSe2 hetero-bilayers

PubMed Central

Zhang, Chendong; Chuu, Chih-Piao; Ren, Xibiao; Li, Ming-Yang; Li, Lain-Jong; Jin, Chuanhong; Chou, Mei-Yin; Shih, Chih-Kang

2017-01-01

By using direct growth, we create a rotationally aligned MoS2/WSe2 hetero-bilayer as a designer van der Waals heterostructure. With rotational alignment, the lattice mismatch leads to a periodic variation of atomic registry between individual van der Waals layers, exhibiting a Moiré pattern with a well-defined periodicity. By combining scanning tunneling microscopy/spectroscopy, transmission electron microscopy, and first-principles calculations, we investigate interlayer coupling as a function of atomic registry. We quantitatively determine the influence of interlayer coupling on the electronic structure of the hetero-bilayer at different critical points. We show that the direct gap semiconductor concept is retained in the bilayer although the valence and conduction band edges are located at different layers. We further show that the local bandgap is periodically modulated in the X-Y direction with an amplitude of ~0.15 eV, leading to the formation of a two-dimensional electronic superlattice. PMID:28070558

Atomic force microscopy of hydrated phosphatidylethanolamine bilayers.

PubMed Central

Zasadzinski, J A; Helm, C A; Longo, M L; Weisenhorn, A L; Gould, S A; Hansma, P K

1991-01-01

We present images of the polar or headgroup regions of bilayers of dimyristoyl-phosphatidylethanolamine (DMPE), deposited by Langmuir-Blodgett deposition onto mica substrates at high surface pressures and imaged under water at room temperature with the optical lever atomic force microscope. The lattice structure of DMPE is visualized with sufficient resolution that the location of individual headgroups can be determined. The forces are sufficiently small that the same area can be repeatedly imaged with a minimum of damage. The DMPE molecules in the bilayer appear to have relatively good long-range orientational order, but rather short-range and poor positional order. These results are in good agreement with x-ray measurements of unsupported lipid monolayers on the water surface, and with electron diffraction of adsorbed monolayers. Images FIGURE 1 FIGURE 2 PMID:2049529

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Jianjun; Cheng, Xiaolin; Heberle, Frederick A

Cholesterol and ether lipids are ubiquitous in mammalian cell membranes, and their interactions are crucial in ether lipid mediated cholesterol trafficking. We report on cholesterol s molecular interactions with ether lipids as determined using a combination of small-angle neutron and Xray scattering, and all-atom molecular dynamics (MD) simulations. A scattering density profile model for an ether lipid bilayer was developed using MD simulations, which was then used to simultaneously fit the different experimental scattering data. From analysis of the data the various bilayer structural parameters were obtained. Surface area constrained MD simulations were also performed to reproduce the experimental data.more » This iterative analysis approach resulted in good agreement between the experimental and simulated form factors. The molecular interactions taking place between cholesterol and ether lipids were then determined from the validated MD simulations. We found that in ether membranes cholesterol primarily hydrogen bonds with the lipid headgroup phosphate oxygen, while in their ester membrane counterparts cholesterol hydrogen bonds with the backbone ester carbonyls. This different mode of interaction between ether lipids and cholesterol induces cholesterol to reside closer to the bilayer surface, dehydrating the headgroup s phosphate moiety. Moreover, the three-dimensional lipid chain spatial density distribution around cholesterol indicates anisotropic chain packing, causing cholesterol to tilt. These insights lend a better understanding of ether lipid-mediated cholesterol trafficking and the roles that the different lipid species have in determining the structural and dynamical properties of membrane associated biomolecules.« less

Interactions between Ether Phospholipids and Cholesterol as Determined by Scattering and Molecular Dynamics Simulations

PubMed Central

Pan, Jianjun; Cheng, Xiaolin; Heberle, Frederick A.; Mostofian, Barmak; Kučerka, Norbert; Drazba, Paul; Katsaras, John

2012-01-01

Cholesterol and ether lipids are ubiquitous in mammalian cell membranes, and their interactions are crucial in ether lipid mediated cholesterol trafficking. We report on cholesterol’s molecular interactions with ether lipids as determined using a combination of small-angle neutron and X-ray scattering, and all-atom molecular dynamics (MD) simulations. A scattering density profile model for an ether lipid bilayer was developed using MD simulations, which was then used to simultaneously fit the different experimental scattering data. From the analysis of the data the various bilayer structural parameters were obtained. Surface area constrained MD simulations were also performed to reproduce the experimental data. This iterative analysis approach resulted in good agreement between the experimental and simulated form factors. The molecular interactions taking place between cholesterol and ether lipids were then determined from the validated MD simulations. We found that in ether membranes, cholesterol primarily hydrogen bonds with the lipid headgroup phosphate oxygen, while in their ester membrane counterparts, cholesterol hydrogen bonds with the backbone ester carbonyls. This different mode of interaction between ether lipids and cholesterol induces cholesterol to reside closer to the bilayer surface, dehydrating the headgroup’s phosphate moiety. Moreover, the three-dimensional lipid chain spatial density distribution around cholesterol indicates anisotropic chain packing, causing cholesterol to tilt. These insights lend a better understanding of ether lipid mediated cholesterol trafficking and the roles that the different lipid species have in determining the structural and dynamical properties of membrane associated biomolecules. PMID:23199292

Atomistic Simulations of Pore Formation and Closure in Lipid Bilayers

PubMed Central

Bennett, W. F. Drew; Sapay, Nicolas; Tieleman, D. Peter

2014-01-01

Cellular membranes separate distinct aqueous compartments, but can be breached by transient hydrophilic pores. A large energetic cost prevents pore formation, which is largely dependent on the composition and structure of the lipid bilayer. The softness of bilayers and the disordered structure of pores make their characterization difficult. We use molecular-dynamics simulations with atomistic detail to study the thermodynamics, kinetics, and mechanism of pore formation and closure in DLPC, DMPC, and DPPC bilayers, with pore formation free energies of 17, 45, and 78 kJ/mol, respectively. By using atomistic computer simulations, we are able to determine not only the free energy for pore formation, but also the enthalpy and entropy, which yields what is believed to be significant new insights in the molecular driving forces behind membrane defects. The free energy cost for pore formation is due to a large unfavorable entropic contribution and a favorable change in enthalpy. Changes in hydrogen bonding patterns occur, with increased lipid-water interactions, and fewer water-water hydrogen bonds, but the total number of overall hydrogen bonds is constant. Equilibrium pore formation is directly observed in the thin DLPC lipid bilayer. Multiple long timescale simulations of pore closure are used to predict pore lifetimes. Our results are important for biological applications, including the activity of antimicrobial peptides and a better understanding of membrane protein folding, and improve our understanding of the fundamental physicochemical nature of membranes. PMID:24411253

Simulations of simple Bovine and Homo sapiens outer cortex ocular lens membrane models with a majority concentration of cholesterol.

PubMed

Adams, Mark; Wang, Eric; Zhuang, Xiaohong; Klauda, Jeffery B

2017-11-21

The lipid composition of bovine and human ocular lens membranes has been probed, and a variety of lipids have been found including phosphatidylcholine (PC), phosphatidylethanolamine (PE), sphingomyelin (SM), and cholesterol (CHOL) with cholesterol being present in particularly high concentrations. In this study, we use the all-atom CHARMM36 force field to simulate binary, ternary, and quaternary mixtures as models of the ocular lens. High concentration of cholesterol, in combination with different and varying diversity of phospholipids (PL) and sphingolipids (SL), affect the structure of the ocular lens lipid bilayer. The following analyses were done for each simulation: surface area per lipid, component surface area per lipid, deuterium order parameters (S CD ), electron density profiles (EDP), membrane thickness, hydrogen bonding, radial distribution functions, clustering, and sterol tilt angle distribution. The S CD show significant bilayer alignment and packing in cholesterol-rich bilayers. The EDP show the transition from liquid crystalline to liquid ordered with the addition of cholesterol. Hydrogen bonds in our systems show the tendency for intramolecular interactions between cholesterol and fully saturated lipid tails for less complex bilayers. But with an increased number of components in the bilayer, the acyl chain of the lipids becomes a less important characteristic, and the headgroup of the lipid becomes more significant. Overall, cholesterol is the driving force of membrane structure of the ocular lens membrane where interactions between cholesterol, PL, and SL determine structure and function of the biomembrane. The goal of this work is to develop a baseline for further study of more physiologically realistic ocular lens lipid membranes. This article is part of a Special Issue entitled: Emergence of Complex Behavior in Biomembranes edited by Marjorie Longo. Copyright © 2017 Elsevier B.V. All rights reserved.

Pressure-induced enhancement in the thermoelectric properties of monolayer and bilayer SnSe2

NASA Astrophysics Data System (ADS)

Zou, Daifeng; Yu, Chuanbin; Li, Yuhao; Ou, Yun; Gao, Yongyi

2018-03-01

The electronic structures of monolayer and bilayer SnSe2 under pressure were investigated by using first-principles calculations including van der Waals interactions. For monolayer SnSe2, the variation of electronic structure under pressure is controlled by pressure-dependent lattice parameters. For bilayer SnSe2, the changes in electronic structure under pressure are dominated by intralayer and interlayer atomic interactions. The n-type thermoelectric properties of monolayer and bilayer SnSe2 under pressure were calculated on the basis of the semi-classical Boltzmann transport theory. It was found that the electrical conductivity of monolayer and bilayer SnSe2 can be enhanced under pressure, and such dependence can be attributed to the pressure-induced changes of the Se-Sn antibonding states in conduction band. Finally, the doping dependence of power factors of n-type monolayer and bilayer SnSe2 at three different pressures were estimated, and the results unveiled that thermoelectric performance of n-type monolayer and bilayer SnSe2 can be improved by applying external pressure. This study benefits to understand the nature of the transport properties for monolayer and bilayer SnSe2 under pressure, and it offers valuable insight for designing high-performance thermoelectric few-layered SnSe2 through strain engineering induced by external pressure.

Pressure-induced enhancement in the thermoelectric properties of monolayer and bilayer SnSe2.

PubMed

Zou, Daifeng; Yu, Chuanbin; Li, Yuhao; Ou, Yun; Gao, Yongyi

2018-03-01

The electronic structures of monolayer and bilayer SnSe 2 under pressure were investigated by using first-principles calculations including van der Waals interactions. For monolayer SnSe 2 , the variation of electronic structure under pressure is controlled by pressure-dependent lattice parameters. For bilayer SnSe 2 , the changes in electronic structure under pressure are dominated by intralayer and interlayer atomic interactions. The n -type thermoelectric properties of monolayer and bilayer SnSe 2 under pressure were calculated on the basis of the semi-classical Boltzmann transport theory. It was found that the electrical conductivity of monolayer and bilayer SnSe 2 can be enhanced under pressure, and such dependence can be attributed to the pressure-induced changes of the Se-Sn antibonding states in conduction band. Finally, the doping dependence of power factors of n -type monolayer and bilayer SnSe 2 at three different pressures were estimated, and the results unveiled that thermoelectric performance of n -type monolayer and bilayer SnSe 2 can be improved by applying external pressure. This study benefits to understand the nature of the transport properties for monolayer and bilayer SnSe 2 under pressure, and it offers valuable insight for designing high-performance thermoelectric few-layered SnSe 2 through strain engineering induced by external pressure.

Free energy of adhesion of lipid bilayers on silica surfaces

NASA Astrophysics Data System (ADS)

Schneemilch, M.; Quirke, N.

2018-05-01

The free energy of adhesion per unit area (hereafter referred to as the adhesion strength) of lipid arrays on surfaces is a key parameter that determines the nature of the interaction between materials and biological systems. Here we report classical molecular simulations of water and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers at model silica surfaces with a range of silanol densities and structures. We employ a novel technique that enables us to estimate the adhesion strength of supported lipid bilayers in the presence of water. We find that silanols on the silica surface form hydrogen bonds with water molecules and that the water immersion enthalpy for all surfaces varies linearly with the surface density of these hydrogen bonds. The adhesion strength of lipid bilayers is a linear function of the surface density of hydrogen bonds formed between silanols and the lipid molecules on crystalline surfaces. Approximately 20% of isolated silanols form such bonds but more than 99% of mutually interacting geminal silanols do not engage in hydrogen bonding with water. On amorphous silica, the bilayer displays much stronger adhesion than expected from the crystalline surface data. We discuss the implications of these results for nanoparticle toxicity.

Modulated phases of phospholipid bilayers induced by tocopherols.

PubMed

Kamal, Md Arif; Raghunathan, V A

2012-11-01

The influence of α-, γ- and δ-tocopherols on the structure and phase behavior of dipalmitoyl phosphatidylcholine (DPPC) bilayers has been determined from X-ray diffraction studies on oriented multilayers. In all the three cases the main-transition temperature (T(m)) of DPPC was found to decrease with increasing tocopherol concentration up to around 25 mol%. Beyond this the main transition is suppressed in the case of γ-tocopherol, whereas T(m) becomes insensitive to composition in the other two cases. The pre-transition is found to be suppressed over a narrow tocopherol concentration range between 7.5 and 10 mol% in DPPC-γ-tocopherol and DPPC-δ-tocopherol bilayers, and the ripple phase occurs down to the lowest temperature studied. In all the three cases a modulated phase is observed above a tocopherol concentration of about 10 mol%, which is similar to the P(β) phase reported in DPPC-cholesterol bilayers. This phase is found to occur even in excess water conditions at lower tocopherol concentrations, and consists of bilayers with periodic height modulation. These results indicate the ability of tocopherols to induce local curvature in membranes, which could be important for some of their biological functions. Copyright © 2012 Elsevier B.V. All rights reserved.

Cyclic and Linear Monoterpenes in Phospholipid Membranes: Phase Behavior, Bilayer Structure, and Molecular Dynamics.

PubMed

Pham, Quoc Dat; Topgaard, Daniel; Sparr, Emma

2015-10-13

Monoterpenes are abundant in essential oils extracted from plants. These relatively small and hydrophobic molecules have shown important biological functions, including antimicrobial activity and membrane penetration enhancement. The interaction between the monoterpenes and lipid bilayers is considered important to the understanding of the biological functions of monoterpenes. In this study, we investigated the effect of cyclic and linear monoterpenes on the structure and dynamics of lipids in model membranes. We have studied the ternary system 1,2-dimyristoyl-sn-glycero-3-phosphocholine-monoterpene-water as a model with a focus on dehydrated conditions. By combining complementary techniques, including differential scanning calorimetry, solid-state nuclear magnetic resonance, and small- and wide-angle X-ray scattering, bilayer structure, phase transitions, and lipid molecular dynamics were investigated at different water contents. Monoterpenes cause pronounced melting point depression and phase segregation in lipid bilayers, and the extent of these effects depends on the hydration conditions. The addition of a small amount of thymol to the fluid bilayer (volume fraction of 0.03 in the bilayer) leads to an increased order in the acyl chain close to the bilayer interface. The findings are discussed in relation to biological systems and lipid formulations.

Adsorption of beryllium atoms and clusters both on graphene and in a bilayer of graphite investigated by DFT.

PubMed

Ferro, Yves; Fernandez, Nicolas; Allouche, Alain; Linsmeier, Christian

2013-01-09

We herein investigate the interaction of beryllium with a graphene sheet and in a bilayer of graphite by means of periodic DFT calculations. In all cases, we find the beryllium atoms to be more weakly bonded on graphene than in the bilayer. Be(2) forms both magnetic and non-magnetic structures on graphene depending on the geometrical configuration of adsorption. We find that the stability of the Be/bilayer system increases with the size of the beryllium clusters inserted into the bilayer of graphite. We also find a charge transfer from beryllium to the graphite layers. All these results are analysed in terms of electronic structure.

Theoretical study on strain induced variations in electronic properties of 2H-MoS{sub 2} bilayer sheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Liang; Dongare, Avinash M., E-mail: dongare@uconn.edu; Namburu, Raju R.

2014-02-03

The strain dependence of the electronic properties of bilayer sheets of 2H-MoS{sub 2} is studied using ab initio simulations based on density functional theory. An indirect band gap for bilayer MoS{sub 2} is observed for all variations of strain along the basal plane. Several transitions for the indirect band gap are observed for various strains for the bilayer structure. The variation of the band gap and the carrier effective masses for the holes and the electrons for the bilayer MoS{sub 2} structure under conditions of uniaxial strain, biaxial strain, as well as uniaxial stress is investigated.

Atomic structure and bonding of the interfacial bilayer between Au nanoparticles and epitaxially regrown MgAl{sub 2}O{sub 4} substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Guo-zhen; Canadian Centre of Electron Microscopy and Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4M1; Majdi, Tahereh

2014-12-08

A unique metal/oxide interfacial bilayer formed between Au nanoparticles and MgAl{sub 2}O{sub 4} substrates following thermal treatment is reported. Associated with the formation of the bilayer was the onset of an abnormal epitaxial growth of the substrate under the nanoparticle. According to the redistribution of atoms and the changes of their electronic structure probed across the interface by a transmission electron microscopy, we suggest two possible atomic models of the interfacial bilayer.

The Impact of Collective Molecular Dynamics on Physiological and Biological Functionalities of Artificial and Biological Membranes

NASA Astrophysics Data System (ADS)

Rheinstadter, Maikel

2008-03-01

We use neutron, X-ray and light scattering techniques to determine dynamical and structural properties of artificial and biological membranes. The combination of various techniques enlarges the window to length scales from the nearest-neighbor distances of lipid molecules to more than 10-6m, covering time scales from about 0.1 ps to 1 s. The main research objective is to quantify collective molecular fluctuations in these systems and to establish relationships to physiological and biological functions of the bilayers, such as transmembrane transport. The motivation for this project is twofold: 1) By understanding fundamental properties of bilayers at the microscopic and mesoscopic level, we aim to tailor membranes with specific properties such as permeability and elasticity. 2) By relating dynamical fluctuations to physiological and biological functions, we can gain a deeper understanding of the bilayers on a molecular scale that may help optimizing the transmembrane transport of certain drugs. We show how bilayer permeability, elasticity and inter protein excitations can be determined from the experiments. M.C. Rheinstädter et al., Phys. Rev. Lett. 93, 108107 (2004); Phys. Rev. Lett. 97, 048103 (2006); Phys. Rev. E 75, 011907 (2007);J. Vac. Soc. Technol. A 24, 1191 (2006).

Examining the origins of the hydration force between lipid bilayers using all-atom simulations.

PubMed

Gentilcore, Anastasia N; Michaud-Agrawal, Naveen; Crozier, Paul S; Stevens, Mark J; Woolf, Thomas B

2010-05-01

Using 237 all-atom double bilayer simulations, we examined the thermodynamic and structural changes that occur as a phosphatidylcholine lipid bilayer stack is dehydrated. The simulated system represents a micropatch of lipid multilayer systems that are studied experimentally using surface force apparatus, atomic force microscopy and osmotic pressure studies. In these experiments, the hydration level of the system is varied, changing the separation between the bilayers, in order to understand the forces that the bilayers feel as they are brought together. These studies have found a curious, strongly repulsive force when the bilayers are very close to each other, which has been termed the "hydration force," though the origins of this force are not clearly understood. We computationally reproduce this repulsive, relatively free energy change as bilayers come together and make qualitative conclusions as to the enthalpic and entropic origins of the free energy change. This analysis is supported by data showing structural changes in the waters, lipids and salts that have also been seen in experimental work. Increases in solvent ordering as the bilayers are dehydrated are found to be essential in causing the repulsion as the bilayers come together.

The Effects of Polyunsaturated Lipid Components on bilayer Structure

NASA Astrophysics Data System (ADS)

Pramudya, Y.; Kiss, A.; Nguyen, Lam T.; Yuan, J.; Hirst, Linda S.

2007-03-01

Polyunsaturated fatty acids (PUFAs), such as DHA (Docosahexanoic Acid) and AA (Alphalinoleic Acid) have been the focus of much research attention in recent years, due to their apparent health benefits and effects on cell physiology. They are found in a variety of biological membranes and have been implicated with lipid raft formation and possible function, particularly in the retinal rod cells and the central nervous system. In this work lipid bilayer structure has been investigated in lipid mixtures, incorporating polyunsaturated fatty acid moieties. The structural effects of increasing concentrations of both symmetric and asymmetric PUFA materials on the bilayer structure are investigated via synchrotron x-ray diffraction on solution samples. We observe bilayer spacings to increase with the percentage of unsaturated fatty acid lipid in the membrane, whilst the degree of ordering significantly decreases. In fact above 20% of fatty acid, well defined bilayers are no longer observed to form. Evidence of phase separation can be clearly seen from these x-ray results and in combination with AFM measurements.

Influence of bilayer resist processing on p-i-n OLEDs: towards multicolor photolithographic structuring of organic displays

NASA Astrophysics Data System (ADS)

Krotkus, Simonas; Nehm, Frederik; Janneck, Robby; Kalkura, Shrujan; Zakhidov, Alex A.; Schober, Matthias; Hild, Olaf R.; Kasemann, Daniel; Hofmann, Simone; Leo, Karl; Reineke, Sebastian

2015-03-01

Recently, bilayer resist processing combined with development in hydrofluoroether (HFE) solvents has been shown to enable single color structuring of vacuum-deposited state-of-the-art organic light-emitting diodes (OLED). In this work, we focus on further steps required to achieve multicolor structuring of p-i-n OLEDs using a bilayer resist approach. We show that the green phosphorescent OLED stack is undamaged after lift-off in HFEs, which is a necessary step in order to achieve RGB pixel array structured by means of photolithography. Furthermore, we investigate the influence of both, double resist processing on red OLEDs and exposure of the devices to ambient conditions, on the basis of the electrical, optical and lifetime parameters of the devices. Additionally, water vapor transmission rates of single and bilayer system are evaluated with thin Ca film conductance test. We conclude that diffusion of propylene glycol methyl ether acetate (PGMEA) through the fluoropolymer film is the main mechanism behind OLED degradation observed after bilayer processing.

Ordering in bio-inorganic hybrid nanomaterials probed by in situ scanning transmission X-ray microscopy

DOE PAGES

Lee, Jonathan R. I.; Bagge-Hansen, Michael; Tunuguntla, Ramya; ...

2015-04-15

Here, phospholipid bilayer coated Si nanowires are one-dimensional (1D) composites that provide versatile bio-nanoelectronic functionality via incorporation of a wide variety of biomolecules into the phospholipid matrix. The physiochemical behaviour of the phospholipid bilayer is strongly dependent on its structure and, as a consequence, substantial modelling and experimental efforts have been directed at the structural characterization of supported bilayers and unsupported phospholipid vesicles; nonetheless, the experimental studies conducted to date have exclusively involved volume-averaged techniques, which do not allow for the assignment of spatially resolved structural variations that could critically impact the performance of the 1D phospholipid-Si NW composites. Inmore » this manuscript, we use scanning transmission X-ray microscopy (STXM) to probe bond orientation and bilayer thickness as a function of position with a spatial resolution of ~30 nm for Δ9-cis 1,2-dioleoyl-sn-glycero-3-phosphocholine layers prepared Si NWs. When coupled with small angle X-ray scattering measurements, the STXM data reveal structural motifs of the Si NWs that give rise to multi-bilayer formation and enable assignment of the orientation of specific bonds known to affect the order and rigidity of phospholipid bilayers.« less

Topological Quantum Phase Transitions in Two-Dimensional Hexagonal Lattice Bilayers

NASA Astrophysics Data System (ADS)

Zhai, Xuechao; Jin, Guojun

2013-09-01

Since the successful fabrication of graphene, two-dimensional hexagonal lattice structures have become a research hotspot in condensed matter physics. In this short review, we theoretically focus on discussing the possible realization of a topological insulator (TI) phase in systems of graphene bilayer (GBL) and boron nitride bilayer (BNBL), whose band structures can be experimentally modulated by an interlayer bias voltage. Under the bias, a band gap can be opened in AB-stacked GBL but is still closed in AA-stacked GBL and significantly reduced in AA- or AB-stacked BNBL. In the presence of spin-orbit couplings (SOCs), further demonstrations indicate whether the topological quantum phase transition can be realized strongly depends on the stacking orders and symmetries of structures. It is observed that a bulk band gap can be first closed and then reopened when the Rashba SOC increases for gated AB-stacked GBL or when the intrinsic SOC increases for gated AA-stacked BNBL. This gives a distinct signal for a topological quantum phase transition, which is further characterized by a jump of the ℤ2 topological invariant. At fixed SOCs, the TI phase can be well switched by the interlayer bias and the phase boundaries are precisely determined. For AA-stacked GBL and AB-stacked BNBL, no strong TI phase exists, regardless of the strength of the intrinsic or Rashba SOCs. At last, a brief overview is given on other two-dimensional hexagonal materials including silicene and molybdenum disulfide bilayers.

Structural, magnetic, and magnetocaloric properties of bilayer manganite La1.38Sr1.62Mn2O7

NASA Astrophysics Data System (ADS)

Yang, Yu-E.; Xie, Yunfei; Xu, Lisha; Hu, Dazhi; Ma, Chunlan; Ling, Langsheng; Tong, Wei; Pi, Li; Zhang, Yuheng; Fan, Jiyu

2018-04-01

In this study, we investigated the structural, magnetic phase transition, and magnetocaloric properties of bilayer perovskite manganite La1.38Sr1.62Mn2O7 based on X-ray diffraction, electron paramagnetic resonance, and temperature-/magnetic field-dependent magnetization measurements. The structural characterization results showed the prepared sample had a tetragonal structure with the space group I4/mmm. The Curie temperature was determined as 114 K in the magnetization studies and a second-order paramagnetic-ferromagnetic transition was confirmed by the Arrott plot, which showed that the slopes were positive for all the curves. According to the variation in the electron paramagnetic resonance spectrum, we detected obvious electronic phase separation across a broad temperature range from 220 to 80 K in this magnetic material, thereby indicating that the paramagnetic and ferromagnetic phases coexist above as well as below the Curie temperature. Based on a plot of the isothermal magnetization versus the magnetic applied field, we deduced the maximum magnetic entropy change, which only reached 1.89 J/kg.K under an applied magnetic field of 7.0 T. These theoretical investigations indicated that in addition to the magnetoelastic couplings and electron interaction, electronic phase separation and anisotropic exchange interactions also affect the magnetic entropy changes in this bilayer manganite.

Diffusional dynamics of an active rhodamine-labeled 1,4-dihydropyridine in sarcolemmal lipid multibilayers.

PubMed Central

Mason, R P; Chester, D W

1989-01-01

A "membrane bilayer pathway" model, involving ligand partition into the bilayer, lateral diffusion, and receptor binding has been invoked to describe the 1,4-dihydropyridine (DHP) calcium channel antagonist receptor binding mechanism. In an earlier study (Chester et al. 1987. Biophys. J. 52:1021-1030), the diffusional component of this model was examined using an active fluorescence labeled DHP calcium channel antagonist, nisoldipine-lissamine rhodamine B (Ns-R), in purified cardiac sarcolemmal (CSL) lipid multibilayers. Diffusion coefficient measurements on membrane-bound drug and phospholipid at maximum bilayer hydration yielded similar values (3.8 x 10(-8) cm2/s). However, decreases in bilayer hydration resulted in dramatically reduced diffusion coefficient values for both probes with substantially greater impact on Ns-R diffusion. These data suggested that hydration dependent diffusional differences could be a function of relative probe location along the bilayer normal. In this communication, we have addressed the relative effect of the rhodamine substituent on Ns-R diffusion complex by examining the diffusional dynamics of free rhodamine B under the same conditions used to evaluate Ns-R complex and phospholipid diffusion. X-ray diffraction studies were performed to determine the Ns-R location in the membrane and model the CSL lipid bilayer profile structure to give a rationale for the differences in probe diffusional dynamics as a function of interbilayer water space. PMID:2611332

Reparameterization of All-Atom Dipalmitoylphosphatidylcholine Lipid Parameters Enables Simulation of Fluid Bilayers at Zero Tension

PubMed Central

Sonne, Jacob; Jensen, Morten Ø.; Hansen, Flemming Y.; Hemmingsen, Lars; Peters, Günther H.

2007-01-01

Molecular dynamics simulations of dipalmitoylphosphatidylcholine (DPPC) lipid bilayers using the CHARMM27 force field in the tensionless isothermal-isobaric (NPT) ensemble give highly ordered, gel-like bilayers with an area per lipid of ∼48 Å2. To obtain fluid (Lα) phase properties of DPPC bilayers represented by the CHARMM energy function in this ensemble, we reparameterized the atomic partial charges in the lipid headgroup and upper parts of the acyl chains. The new charges were determined from the electron structure using both the Mulliken method and the restricted electrostatic potential fitting method. We tested the derived charges in molecular dynamics simulations of a fully hydrated DPPC bilayer. Only the simulation with the new restricted electrostatic potential charges shows significant improvements compared with simulations using the original CHARMM27 force field resulting in an area per lipid of 60.4 ± 0.1 Å2. Compared to the 48 Å2, the new value of 60.4 Å2 is in fair agreement with the experimental value of 64 Å2. In addition, the simulated order parameter profile and electron density profile are in satisfactory agreement with experimental data. Thus, the biologically more interesting fluid phase of DPPC bilayers can now be simulated in all-atom simulations in the NPT ensemble by employing our modified CHARMM27 force field. PMID:17400696

Modeling the Effects of Lipid Composition on Stratum Corneum Bilayers Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Huzil, J. Torin; Sivaloganathan, Siv; Kohandel, Mohammad; Foldvari, Marianna

2011-11-01

The advancement of dermal and transdermal drug delivery requires the development of delivery systems that are suitable for large protein and nucleic acid-based therapeutic agents. However, a complete mechanistic understanding of the physical barrier properties associated with the epidermis, specifically the membrane structures within the stratum corneum, has yet to be developed. Here, we describe the assembly and computational modeling of stratum corneum lipid bilayers constructed from varying ratios of their constituent lipids (ceramide, free fatty acids and cholesterol) to determine if there is a difference in the physical properties of stratum corneum compositions.

Periodic minimal surface organizations of the lipid bilayer at the lung surface and in cubic cytomembrane assemblies.

PubMed

Larsson, Marcus; Larsson, Kåre

2014-03-01

The existence of infinite periodic lipid bilayer structures in biological systems was first demonstrated in cell membrane assemblies. Such periodicity is only possible in symmetric bilayers, and their occurrence is discussed here in relation to the asymmetry of cell membranes in vivo. A periodic membrane conformation in the prolamellar body of plants corresponds to a dormant state without photosynthesis. A similar reversible formation of a dormant state has also been observed in the mitochondria of the amoeba Chaos. In these cases the energy production has become insufficient to maintain the membrane asymmetry. Formation of membranes that are symmetric over the bilayer is proposed to be a principal mechanism behind formation of cubic membrane systems. Another type of bicontinuous minimal surface structure is considered to form the alveolar lining of mammals at normal breathing conditions. The CLP surface corresponds to such a tetragonal surface phase. It is also a symmetric bilayer and in a state of zero energy expenditure. Structural alternatives of the bilayer conformation in this latter system are also discussed here. © 2013 Elsevier B.V. All rights reserved.

Ab-initio calculation of electronic structure and optical properties of AB-stacked bilayer α-graphyne

NASA Astrophysics Data System (ADS)

Behzad, Somayeh

2016-09-01

Monolayer α-graphyne is a new two-dimensional carbon allotrope with many special features. In this work the electronic properties of AA- and AB-stacked bilayers of this material and then the optical properties are studied, using first principle plane wave method. The electronic spectrum has two Dirac cones for AA stacked bilayer α-graphyne. For AB-stacked bilayer, the interlayer interaction changes the linear bands into parabolic bands. The optical spectra of the most stable AB-stacked bilayer closely resemble to that of the monolayer, except for small shifts of peak positions and increasing of their intensity. For AB-stacked bilayer, a pronounced peak has been found at low energies under the perpendicular polarization. This peak can be clearly ascribed to the transitions at the Dirac point as a result of the small degeneracy lift in the band structure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tran, Ich C.; Tunuguntla, Ramya H.; Kim, Kyunghoon

Carbon nanotube porins (CNTPs), small segments of carbon nanotubes capable of forming defined pores in lipid membranes, are important future components for bionanoelectronic devices as they could provide a robust analog of biological membrane channels. Furthermore, in order to control the incorporation of these CNT channels into lipid bilayers, it is important to understand the structure of the CNTPs before and after insertion into the lipid bilayer as well as the impact of such insertion on the bilayer structure. Here we employed a noninvasive in situ probe, small-angle X-ray scattering, to study the integration of CNT porins into dioleoylphosphatidylcholine bilayers.more » These results show that CNTPs in solution are stabilized by a monolayer of lipid molecules wrapped around their outer surface. We also demonstrate that insertion of CNTPs into the lipid bilayer results in decreased bilayer thickness with the magnitude of this effect increasing with the concentration of CNTPs.« less

Synthesis and Characterization of Novel Anchorlipids for Tethered Bilayer Lipid Membranes.

PubMed

Andersson, Jakob; Knobloch, Jacqueline J; Perkins, Michael V; Holt, Stephen A; Köper, Ingo

2017-05-09

Tethered bilayer lipid membranes are versatile solid-supported model membrane systems. Core to these systems is an anchorlipid that covalently links a lipid bilayer to a support. The molecular structure of these lipids can have a significant impact on the properties of the resulting bilayer. Here, the synthesis of anchorlipids containing ester groups in the tethering part is described. The lipids are used to form bilayer membranes, and the resulting structures are compared with membranes formed using conventional anchorlipids or sparsely tethered membranes. All membranes showed good electrical sealing properties; the disulphide-terminated anchorlipids could be used in a sparsely tethered system without significantly reducing the sealing properties of the lipid bilayers. The sparsely tethered systems also allowed for higher ion transport across the membrane, which is in good correlation with higher hydration of the spacer region as seen by neutron scattering.

Longitudinal Proximity Effect, Lateral Inverse Proximity Effect, and Nonequilibrium Superconductivity in Transition-edge Sensors

NASA Technical Reports Server (NTRS)

Sadleir, John E.

2010-01-01

We have recently shown that normal-metal/superconductor (N/S) bilayer TESs (superconducting Transition-Edge Sensors) exhibit weak-link behavior. Our measurements were explained in terms of a longitudinal proximity effect model in which superconducting order from the higher transition temperature leads is induced into the TES bilayer plane over remarkably long distances (up to 290 micron). Here we extend our understanding to include TESs with added noise-mitigating normal-metal structures (N structures). We explain our results of an effect converse to the longitudinal proximity effect (LoPE), the lateral inverse proximity effect (LaiPE), for which the order parameter in the N/S bilayer is reduced due to the neighboring N structures. We present resistance and critical current measurements as a function of temperature and magnetic field taken on square Mo/Au bilayer TESs with lengths ranging from 8 to 130 micron with and without added N structures. We observe the inverse proximity effect on the bilayer over in-plane distances many tens of microns and find the transition shifts to lower temperature scale approximately as the inverse square of the in-plane N-structure separation distance, without appreciable broadening of the transition width. We find TESs with added Au structures exhibit weak-link behavior as evidenced by exponential temperature dependence of the critical current and Josephson-like oscillations of the critical current with applied magnetic field. We also present evidence for nonequilbrium superconductivity and estimate a quasiparticle lifetime of 1.8 x 10(exp -10) s for the bilayer. The LoPE model is also used to explain the increased conductivity at temperatures above the bilayer's steep resistive transition

Longitudinal Proximity Effect, Lateral Inverse Proximity Effect, and Nonequilibrium Superconductivity in Transition-Edge Sensors

NASA Technical Reports Server (NTRS)

Sadleir, John E.

2010-01-01

We have recently shown that normal-metal/superconductor (N /S) bilayer TESs (superconducting Transition-Edge Sensors) exhibit weak-link behavior. Our measurements were explained in terms of a longitudinal proximity effect model in which superconducting order from the higher transition temperature leads is induced into the TES bilayer plane over remarkably long distances (up to 290 micron). Here we extend our understanding to include TESs with added noise-mitigating normal-metal structures (N structures). We explain our results in terms of an effect converse to the longitudinal proximity effect (LoPE), the lateral inverse proximity effect (LaiPE), for which the order parameter in the N /S bilayer is reduced due to the neighboring N structures. We present resistance and critical current measurements as a function of temperature and magnetic field taken on square Mo/Au bilayer TESs with lengths ranging from 8 to 130 micron with and without added N structures. We observe the inverse proximity effect on the bilayer over in-plane distances many tens of microns and find the transition shifts to lower temperatures scale approximately as the inverse square of the in-plane N-structure separation distance, without appreciable broadening of the transition width. We find TESs with added Au structures exhibit weak-link behavior as evidenced by exponential temperature dependence of the critical current and Josephson-like oscillations of the critical current with applied magnetic field. We also present evidence for nonequilbrium superconductivity and estimate a quasiparticle lifetime of 1.8 x 10(exp -10) s for the bilayer. The LoPE model is also used to explain the increased conductivity at temperatures above the bilayer's steep resistive transition.

Measuring Interlayer Shear Stress in Bilayer Graphene

NASA Astrophysics Data System (ADS)

Wang, Guorui; Dai, Zhaohe; Wang, Yanlei; Tan, PingHeng; Liu, Luqi; Xu, Zhiping; Wei, Yueguang; Huang, Rui; Zhang, Zhong

2017-07-01

Monolayer two-dimensional (2D) crystals exhibit a host of intriguing properties, but the most exciting applications may come from stacking them into multilayer structures. Interlayer and interfacial shear interactions could play a crucial role in the performance and reliability of these applications, but little is known about the key parameters controlling shear deformation across the layers and interfaces between 2D materials. Herein, we report the first measurement of the interlayer shear stress of bilayer graphene based on pressurized microscale bubble loading devices. We demonstrate continuous growth of an interlayer shear zone outside the bubble edge and extract an interlayer shear stress of 40 kPa based on a membrane analysis for bilayer graphene bubbles. Meanwhile, a much higher interfacial shear stress of 1.64 MPa was determined for monolayer graphene on a silicon oxide substrate. Our results not only provide insights into the interfacial shear responses of the thinnest structures possible, but also establish an experimental method for characterizing the fundamental interlayer shear properties of the emerging 2D materials for potential applications in multilayer systems.

Structure of the ripple phase in lecithin bilayers.

PubMed Central

Sun, W J; Tristram-Nagle, S; Suter, R M; Nagle, J F

1996-01-01

The phases of the x-ray form factors are derived for the ripple (Pbeta') thermodynamic phase in the lecithin bilayer system. By combining these phases with experimental intensity data, the electron density map of the ripple phase of dimyristoyl-phosphatidylcholine is constructed. The phases are derived by fitting the intensity data to two-dimensional electron density models, which are created by convolving an asymmetric triangular ripple profile with a transbilayer electron density profile. The robustness of the model method is indicated by the result that many different models of the transbilayer profile yield essentially the same phases, except for the weaker, purely ripple (0,k) peaks. Even with this residual ambiguity, the ripple profile is well determined, resulting in 19 angstroms for the ripple amplitude and 10 degrees and 26 degrees for the slopes of the major and the minor sides, respectively. Estimates for the bilayer head-head spacings show that the major side of the ripple is consistent with gel-like structure, and the minor side appears to be thinner with lower electron density. Images Fig. 1 Fig. 2 PMID:8692934

TiCN/TiNbCN multilayer coatings with enhanced mechanical properties

NASA Astrophysics Data System (ADS)

Caicedo, J. C.; Amaya, C.; Yate, L.; Gómez, M. E.; Zambrano, G.; Alvarado-Rivera, J.; Muñoz-Saldaña, J.; Prieto, P.

2010-08-01

Enhancement of mechanical properties by using a TiCN/TiNbCN multilayered system with different bilayer periods ( Λ) and bilayer numbers ( n) via magnetron sputtering technique was studied in this work. The coatings were characterized in terms of structural, chemical, morphological and mechanical properties by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nanoindentation. Results of the X-ray analysis showed reflections associated to FCC (1 1 1) crystal structure for TiCN/TiNbCN films. AFM analysis revealed a reduction of grain size and roughness when the bilayer number is increased and the bilayer period is decreased. Finally, enhancement of mechanical properties was determined via nanoindentation measurements. The best behavior was obtained when the bilayer period ( Λ) was 15 nm ( n = 200), yielding the highest hardness (42 GPa) and elastic modulus (408 GPa). The values for the hardness and elastic modulus are 1.6 and 1.3 times greater than the coating with n = 1, respectively. The enhancement effects in multilayer coatings could be attributed to different mechanisms for layer formation with nanometric thickness due to the Hall-Petch effect; because this effect, originally used to explain the increase in hardness with decreasing grain size in bulk polycrystalline metals, has also been used to explain hardness enhancements in multilayers taking into account the thickness reduction at individual single layers that make the multilayered system. The Hall-Petch model based on dislocation motion within layers and across layer interfaces, has been successfully applied to multilayers to explain this hardness enhancement.

Membrane insertion of fusion peptides from Ebola and Marburg viruses studied by replica-exchange molecular dynamics simulations.

PubMed

Olson, Mark A; Lee, Michael S; Yeh, In-Chul

2017-06-15

This work presents replica-exchange molecular dynamics simulations of inserting a 16-residue Ebola virus fusion peptide into a membrane bilayer. A computational approach is applied for modeling the peptide at the explicit all-atom level and the membrane-aqueous bilayer by a generalized Born continuum model with a smoothed switching function (GBSW). We provide an assessment of the model calculations in terms of three metrics: (1) the ability to reproduce the NMR structure of the peptide determined in the presence of SDS micelles and comparable structural data on other fusion peptides; (2) determination of the effects of the mutation Trp-8 to Ala and sequence discrimination of the homologous Marburg virus; and (3) calculation of potentials of mean force for estimating the partitioning free energy and their comparison to predictions from the Wimley-White interfacial hydrophobicity scale. We found the GBSW implicit membrane model to produce results of limited accuracy in conformational properties of the peptide when compared to the NMR structure, yet the model resolution is sufficient to determine the effect of sequence differentiation on peptide-membrane integration. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Shock-induced poration, cholesterol flip-flop and small interfering RNA transfection in a phospholipid membrane: Multimillion atom, microsecond molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Choubey, Amit

Biological cell membranes provide mechanical stability to cells and understanding their structure, dynamics and mechanics are important biophysics problems. Experiments coupled with computational methods such as molecular dynamics (MD) have provided insight into the physics of membranes. We use long-time and large-scale MD simulations to study the structure, dynamics and mechanical behavior of membranes. We investigate shock-induced collapse of nanobubbles in water using MD simulations based on a reactive force field. We observe a focused jet at the onset of bubble shrinkage and a secondary shock wave upon bubble collapse. The jet length scales linearly with the nanobubble radius, as observed in experiments on micron-to-millimeter size bubbles. Shock induces dramatic structural changes, including an ice-VII-like structural motif at a particle velocity of 1 km/s. The incipient ice VII formation and the calculated Hugoniot curve are in good agreement with experimental results. We also investigate molecular mechanisms of poration in lipid bilayers due to shock-induced collapse of nanobubbles. Our multimillion-atom MD simulations reveal that the jet impact generates shear flow of water on bilayer leaflets and pressure gradients across them. This transiently enhances the bilayer permeability by creating nanopores through which water molecules translocate rapidly across the bilayer. Effects of nanobubble size and temperature on the porosity of lipid bilayers are examined. The second research project focuses on cholesterol (CHOL) dynamics in phospholipid bilayers. Several experimental and computational studies have been performed on lipid bilayers consisting of dipalmitoylphosphatidylcholine (DPPC) and CHOL molecules. CHOL interleaflet transport (flip-flop) plays an important role in interleaflet coupling and determining CHOL flip-flop rate has been elusive. Various studies report that the rate ranges between milliseconds to seconds. We calculate CHOL flip-flop rates by performing a 15 mus all-atom MD simulation of a DPPC-CHOL bilayer. We find that the CHOL flip-flop rates are on the sub microsecond timescale. These results are verified by performing various independent parallel replica (PR) simulations. Our PR simulations provide significant boost in sampling of the flip-flop events. We observe that the CHOL flip-flop can induce membrane order, regulate membrane-bending energy, and facilitate membrane relaxation. The rapid flip-flop rates reported here have important implications for the role of CHOL in mechanical properties of cell membranes, formation of domains, and maintaining CHOL concentration asymmetry in plasma membrane. Our PR approach can reach submillisecond time scales and bridge the gap between MD simulations and Nuclear Magnetic Resonance (NMR) experiments on CHOL flip-flop dynamics in membranes. The last project deals with transfection barriers encountered by a bare small interfering RNA (siRNA) in a phospholipid bilayer. SiRNA molecules play a pivotal role in therapeutic applications. A key limitation to the widespread implementation of siRNA-based therapeutics is the difficulty of delivering siRNA-based drugs to cells. We have examined structural and mechanical barriers to siRNA passage across a phospholipid bilayer using all-atom MD simulations. We find that the electrostatic interaction between the anionic siRNA and head groups of phospholipid molecules induces a phase transformation from the liquid crystalline to ripple phase. Steered MD simulations reveal that the siRNA transfection through the ripple phase requires a force of ˜ 1.5 nN.

Translocation Thermodynamics of Linear and Cyclic Nonaarginine into Model DPPC Bilayer via Coarse-Grained Molecular Dynamics Simulation: Implications of Pore Formation and Nonadditivity

PubMed Central

2015-01-01

Structural mechanisms and underlying thermodynamic determinants of efficient internalization of charged cationic peptides (cell-penetrating peptides, CPPs) such as TAT, polyarginine, and their variants, into cells, cellular constructs, and model membrane/lipid bilayers (large and giant unilamellar or multilamelar vesicles) continue to garner significant attention. Two widely held views on the translocation mechanism center on endocytotic and nonendocytotic (diffusive) processes. Espousing the view of a purely diffusive internalization process (supported by recent experimental evidence, [Säälik, P.; et al. J. Controlled Release2011, 153, 117–125]), we consider the underlying free energetics of the translocation of a nonaarginine peptide (Arg9) into a model DPPC bilayer. In the case of the Arg9 cationic peptide, recent experiments indicate a higher internalization efficiency of the cyclic structure (cyclic Arg9) relative to the linear conformer. Furthermore, recent all-atom resolution molecular dynamics simulations of cyclic Arg9 [Huang, K.; et al. Biophys. J., 2013, 104, 412–420] suggested a critical stabilizing role of water- and lipid-constituted pores that form within the bilayer as the charged Arg9 translocates deep into the bilayer center. Herein, we use umbrella sampling molecular dynamics simulations with coarse-grained Martini lipids, polarizable coarse-grained water, and peptide to explore the dependence of translocation free energetics on peptide structure and conformation via calculation of potentials of mean force along preselected reaction paths allowing and preventing membrane deformations that lead to pore formation. Within the context of the coarse-grained force fields we employ, we observe significant barriers for Arg9 translocation from bulk aqueous solution to bilayer center. Moreover, we do not find free-energy minima in the headgroup–water interfacial region, as observed in simulations using all-atom force fields. The pore-forming paths systematically predict lower free-energy barriers (ca. 90 kJ/mol lower) than the non pore-forming paths, again consistent with all-atom force field simulations. The current force field suggests no preference for the more compact or covalently cyclic structures upon entering the bilayer. Decomposition of the PMF into the system’s components indicates that the dominant stabilizing contribution along the pore-forming path originates from the membrane as both layers of it deformed due to the formation of pore. Furthermore, our analysis revealed that although there is significant entropic stabilization arising from the enhanced configurational entropy exposing more states as the peptide moves through the bilayer, the enthalpic loss (as predicted by the interactions of this coarse-grained model) far outweighs any former stabilization, thus leading to significant barrier to translocation. Finally, we observe reduction in the translocation free-energy barrier for a second Arg9 entering the bilayer in the presence of an initial peptide restrained at the center, again, in qualitative agreement with all-atom force fields. PMID:24506488

Structure and Thermotropic phase Behavior of Fluorinated Phospholipid Bilayers: A combined Attenuated Total Reflection FTIR Spectroscopy and Imaging Ellipsometry Study

PubMed Central

Schuy, Steffen; Faiss, Simon; Yoder, Nicholas C.; Kalsani, Venkateshwarlu; Kumar, Krishna; Janshoff, Andreas; Vogel, Reiner

2008-01-01

Lipid bilayers consisting of lipids with terminally perfluoroalkylated chains have remarkable properties. They exhibit increased stability and phase-separated nanoscale patterns in mixtures with nonfluorinated lipids. In order to understand the bilayer properties that are responsible for this behavior, we have analyzed the structure of solid-supported bilayers composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and of a DPPC analogue with 6 terminal perfluorinated methylene units (F6-DPPC). Polarized attenuated total reflection Fourier-transform infrared spectroscopy indicates that for F6-DPPC, the tilt of the lipid acyl chains to the bilayer normal is increased to 39° as compared to 21° for native DPPC, for both lipids in the gel phase. This substantial increase of the tilt angle is responsible for a decrease of the bilayer thickness from 5.4 nm for DPPC to 4.5 nm for F6-DPPC, as revealed by temperature-controlled imaging ellipsometry on microstructured lipid bilayers and solution atomic force microscopy. During the main phase transition from the gel to the fluid phase, both the relative bilayer thickness change and the relative area change are substantially smaller for F6-DPPC than for DPPC. In light of these structural and thermotropic data, we propose a model in which the higher acyl-chain tilt angle in F6-DPPC is the result of a conformational rearrangement to minimize unfavorable fluorocarbon–hydrocarbon interactions in the center of the bilayer due to chain staggering. PMID:18563929

Quantitative Raman microspectroscopy for water permeability parameters at a droplet interface bilayer.

PubMed

Braziel, S; Sullivan, K; Lee, S

2018-01-29

Using confocal Raman microspectroscopy, we derive parameters for bilayer water transport across an isolated nanoliter aqueous droplet pair. For a bilayer formed with two osmotically imbalanced and adherent nanoliter aqueous droplets in a surrounding oil solvent, a droplet interface bilayer (DIB), the water permeability coefficient across the lipid bilayer was determined from monitoring the Raman scattering from the C[triple bond, length as m-dash]N stretching mode of K 3 Fe(CN) 6 as a measure of water uptake into the swelling droplet of a DIB pair. We also derive passive diffusional permeability coefficient for D 2 O transport across a droplet bilayer using O-D Raman signal. This method provides a significant methodological advance in determining water permeability coefficients in a convenient and reliable way.

Effects of van der Waals interaction and electric field on the electronic structure of bilayer MoS2.

PubMed

Xiao, Jin; Long, Mengqiu; Li, Xinmei; Zhang, Qingtian; Xu, Hui; Chan, K S

2014-10-08

The modification of the electronic structure of bilayer MoS2 by an external electric field can have potential applications in optoelectronics and valleytronics. Nevertheless, the underlying physical mechanism is not clearly understood, especially the effects of the van der Waals interaction. In this study, the spin orbit-coupled electronic structure of bilayer MoS2 has been investigated using the first-principle density functional theory. We find that the van der Waals interaction as well as the interlayer distance has significant effects on the band structure. When the interlayer distance of bilayer MoS2 increases from 0.614 nm to 0.71 nm, the indirect gap between the Γ and Λ points increases from 1.25 eV to 1.70 eV. Meanwhile, the energy gap of bilayer MoS2 transforms from an indirect one to a direct one. An external electric field can shift down (up) the energy bands of the bottom (top) MoS2 layer and also breaks the inversion symmetry of bilayer MoS2. As a result, the electric field can affect the band gaps, the spin-orbit interaction and splits the valance bands into two groups. The present study can help us understand more about the electronic structures of MoS2 materials for potential applications in electronics and optoelectronics.

Phase transition behaviors of the supported DPPC bilayer investigated by sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM).

PubMed

Wu, Heng-Liang; Tong, Yujin; Peng, Qiling; Li, Na; Ye, Shen

2016-01-21

The phase transition behaviors of a supported bilayer of dipalmitoylphosphatidyl-choline (DPPC) have been systematically evaluated by in situ sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM). By using an asymmetric bilayer composed of per-deuterated and per-protonated monolayers, i.e., DPPC-d75/DPPC and a symmetric bilayer of DPPC/DPPC, we were able to probe the molecular structural changes during the phase transition process of the lipid bilayer by SFG spectroscopy. It was found that the DPPC bilayer is sequentially melted from the top (adjacent to the solution) to bottom leaflet (adjacent to the substrate) over a wide temperature range. The conformational ordering of the supported bilayer does not decrease (even slightly increases) during the phase transition process. The conformational defects in the bilayer can be removed after the complete melting process. The phase transition enthalpy for the bottom leaflet was found to be approximately three times greater than that for the top leaflet, indicating a strong interaction of the lipids with the substrate. The present SFG and AFM observations revealed similar temperature dependent profiles. Based on these results, the temperature-induced structural changes in the supported lipid bilayer during its phase transition process are discussed in comparison with previous studies.

Ordered and layered structure of liquid nitromethane within a graphene bilayer: toward stabilization of energetic materials through nanoscale confinement.

PubMed

Liu, Yingzhe; Yu, Tao; Lai, Weipeng; Kang, Ying; Ge, Zhongxue

2015-03-01

The structural characteristics involving thermal stabilities of liquid nitromethane (NM)—one of the simplest energetic materials—confined within a graphene (GRA) bilayer were investigated by means of all-atom molecular dynamics simulations and density functional theory calculations. The results show that ordered and layered structures are formed at the confinement of the GRA bilayer induced by the van der Waals attractions of NM with GRA and the dipole-dipole interactions of NM, which is strongly dependent on the confinement size, i.e., the GRA bilayer distance. These unique intermolecular arrangements and preferred orientations of confined NM lead to higher stabilities than bulk NM revealed by bond dissociation energy calculations.

Proximity Effects and Nonequilibrium Superconductivity in Transition-Edge Sensors

NASA Technical Reports Server (NTRS)

Sadleir, John E.; Smith, Stephen J.; Robinson, Ian K.; Finkbeiner, Fred M.; Chervenak, James A.; Bandler, Simon R.; Eckart, Megan E.; Kilbourne, Caroline A.

2011-01-01

We have recently shown that normal-metal/superconductor (N/S) bilayer TESs (superconducting Transition-Edge Sensors) exhibit weak-link behavior.l Here we extend our understanding to include TESs with added noise-mitigating normal-metal structures (N structures). We find TESs with added Au structures also exhibit weak-link behavior as evidenced by exponential temperature dependence of the critical current and Josephson-like oscillations of the critical current with applied magnetic field. We explain our results in terms of an effect converse to the longitudinal proximity effect (LoPE) 1, the lateral inverse proximity effect (LaiPE), for which the order parameter in the N/S bilayer is reduced due to the neighboring N structures. Resistance and critical current measurements are presented as a function of temperature and magnetic field taken on square Mol Au bilayer TESs with lengths ranging from 8 to 130 {\\mu}m with and without added N structures. We observe the inverse proximity effect on the bilayer over in-plane distances many tens of microns and find the transition shifts to lower temperatures scale approximately as the inverse square of the in- plane N-structure separation distance, without appreciable broadening of the transition width. We also present evidence for nonequilbrium superconductivity and estimate a quasiparticle lifetime of 1.8 \\times 10-10 s for the bilayer. The LoPE model is also used to explain the increased conductivity at temperatures above the bilayer's steep resistive transition.

Phospholipid bilayer affinities and solvation characteristics by electrokinetic chromatography with a nanodisc pseudostationary phase.

PubMed

Penny, William M; Steele, Harmen B; Ross, J B Alexander; Palmer, Christopher P

2017-03-01

Phospholipid bilayer nanodiscs composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine and synthetic maleic acid-styrene copolymer belts have been introduced as a pseudostationary phase (PSP) in electrokinetic chromatography and demonstrated good performance. The nanodiscs provide a suitable migration range and high theoretical plate counts. Using this nanodisc pseudostationary phase, the affinity of the bilayer structure for probe solutes was determined and characterized. Good correlation is observed between retention factors and octanol water partition coefficients for particular categories of solutes, but the general correlation is weak primarily because the nanodiscs show stronger affinity than octanol for hydrogen bond donors. This suggests that a more appropriate application of this technology is to measure and characterize interactions between solutes and lipid bilayers directly. Linear solvation energy relationship analysis of the nanodisc-solute interactions in this study demonstrates that the nanodiscs provide a solvation environment with low cohesivity and weak hydrogen bond donating ability, and provide relatively strong hydrogen bond acceptor strength. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

All-atom simulations and free-energy calculations of coiled-coil peptides with lipid bilayers: binding strength, structural transition, and effect on lipid dynamics

NASA Astrophysics Data System (ADS)

Woo, Sun Young; Lee, Hwankyu

2016-03-01

Peptides E and K, which are synthetic coiled-coil peptides for membrane fusion, were simulated with lipid bilayers composed of lipids and cholesterols at different ratios using all-atom models. We first calculated free energies of binding from umbrella sampling simulations, showing that both E and K peptides tend to adsorb onto the bilayer surface, which occurs more strongly in the bilayer composed of smaller lipid headgroups. Then, unrestrained simulations show that K peptides more deeply insert into the bilayer with partially retaining the helical structure, while E peptides less insert and predominantly become random coils, indicating the structural transition from helices to random coils, in quantitative agreement with experiments. This is because K peptides electrostatically interact with lipid phosphates, as well as because hydrocarbons of lysines of K peptide are longer than those of glutamic acids of E peptide and thus form stronger hydrophobic interactions with lipid tails. This deeper insertion of K peptide increases the bilayer dynamics and a vacancy below the peptide, leading to the rearrangement of smaller lipids. These findings help explain the experimentally observed or proposed differences in the insertion depth, binding strength, and structural transition of E and K peptides, and support the snorkeling effect.

Bi-layer plate-type acoustic metamaterials with Willis coupling

NASA Astrophysics Data System (ADS)

Ma, Fuyin; Huang, Meng; Xu, Yicai; Wu, Jiu Hui

2018-01-01

Dynamic effective negative parameters are principal to the representation of the physical properties of metamaterials. In this paper, a bi-layer plate-type unit was proposed with both a negative mass density and a negative bulk modulus; moreover, through analysis of these bi-layer structures, some important problems about acoustic metamaterials were studied. First, dynamic effective mass densities and the bulk modulus of the bi-layer plate-type acoustic structure were clarified through both the direct and the retrieval methods, and, in addition, the intrinsic relationship between the sound transmission (absorption) characteristics and the effective parameters was analyzed. Furthermore, the properties of dynamic effective parameters for an asymmetric bi-layer acoustic structure were further considered through an analysis of experimental data, and the modified effective parameters were then obtained through consideration of the Willis coupling in the asymmetric passive system. In addition, by taking both the clamped and the periodic boundary conditions into consideration in the bi-layer plate-type acoustic system, new perspectives were presented for study on the effective parameters and sound insulation properties in the range below the cut-off frequency. The special acoustic properties established by these effective parameters could enrich our knowledge and provide guidance for the design and installation of acoustic metamaterial structures in future sound engineering practice.

All-atom simulations and free-energy calculations of coiled-coil peptides with lipid bilayers: binding strength, structural transition, and effect on lipid dynamics.

PubMed

Woo, Sun Young; Lee, Hwankyu

2016-03-01

Peptides E and K, which are synthetic coiled-coil peptides for membrane fusion, were simulated with lipid bilayers composed of lipids and cholesterols at different ratios using all-atom models. We first calculated free energies of binding from umbrella sampling simulations, showing that both E and K peptides tend to adsorb onto the bilayer surface, which occurs more strongly in the bilayer composed of smaller lipid headgroups. Then, unrestrained simulations show that K peptides more deeply insert into the bilayer with partially retaining the helical structure, while E peptides less insert and predominantly become random coils, indicating the structural transition from helices to random coils, in quantitative agreement with experiments. This is because K peptides electrostatically interact with lipid phosphates, as well as because hydrocarbons of lysines of K peptide are longer than those of glutamic acids of E peptide and thus form stronger hydrophobic interactions with lipid tails. This deeper insertion of K peptide increases the bilayer dynamics and a vacancy below the peptide, leading to the rearrangement of smaller lipids. These findings help explain the experimentally observed or proposed differences in the insertion depth, binding strength, and structural transition of E and K peptides, and support the snorkeling effect.

Variations of thermoelectric performance by electric fields in bilayer MX2 (M = W, Mo; X = S, Se).

PubMed

Wang, Rui-Ning; Dong, Guo-Yi; Wang, Shu-Fang; Fu, Guang-Sheng; Wang, Jiang-Long

2017-02-22

A gate electrode is usually used to controllably tune the carrier concentrations, further modulating the electrical conductivity and the Seebeck coefficient to obtain the optimum thermoelectric figure of merit (ZT) in two-dimensional materials. On the other hand, it is necessary to investigate how an electric field induced by a gate voltage affects the electronic structures, further determining the thermoelectric properties. Therefore, by using density functional calculations in combination with Boltzmann theory, the thermoelectric properties of bilayer MX 2 (M = W, Mo; X = S, Se) with or without a 1 V nm -1 perpendicular electric field are comparatively investigated. First of all, the variations of the electrical conductivity (σ), electron thermal conductivity and Seebeck coefficient (S) with the carrier concentration are studied. Due to the trade-off relationship between S and σ, there is an optimum concentration to obtain the maximum ZT, which increases with the temperature due to the enhancement of the Seebeck coefficient. Moreover, N-type bilayers have larger optimum ZTs than P-type bilayers. In addition, the electric field results in the increase of the Seebeck coefficient in low hole-doped MS 2 bilayers and high hole-doped MSe 2 bilayers, thus leading to similar variations in ZT. The optimum ZTs are reduced from 2.11 × 10 -2 , 3.19 × 10 -2 , 2.47 × 10 -2 , and 2.58 × 10 -2 to 1.57 × 10 -2 , 1.51 × 10 -2 , 2.08 × 10 -2 , and 1.43 × 10 -2 for the hole-doped MoS 2 , MoSe 2 , and WSe 2 bilayers, respectively. For N-type bilayers, the electric field shows a destructive effect, resulting in the obvious reduction of the Seebeck coefficient in the MSe 2 layers and the low electron-doped MS 2 bilayers. In electron-doped bilayers, the optimum ZTs will decrease from 3.03 × 10 -2 , 6.64 × 10 -2 , and 6.69 × 10 -2 to 2.81 × 10 -2 , 3.59 × 10 -2 , and 4.39 × 10 -2 for the MoS 2 , MoSe 2 , and WSe 2 bilayers, respectively.

Neutron reflecting supermirror structure

DOEpatents

Wood, James L.

1992-01-01

An improved neutron reflecting supermirror structure comprising a plurality of stacked sets of bilayers of neutron reflecting materials. The improved neutron reflecting supermirror structure is adapted to provide extremely good performance at high incidence angles, i.e. up to four time the critical angle of standard neutron mirror structures. The reflection of neutrons striking the supermirror structure at a high critical angle provides enhanced neutron throughput, and hence more efficient and economical use of neutron sources. One layer of each set of bilayers consist of titanium, and the second layer of each set of bilayers consist of an alloy of nickel with carbon interstitially present in the nickel alloy.

Free energy simulations of amylin I26P mutation in a lipid bilayer.

PubMed

Jalili, Seifollah; Maleki, Afsaneh; Akhavan, Mojdeh; Najafi, Bijan; Schofield, Jeremy

2015-02-01

The amylin peptide in a dioleoylphosphatidylcholine (DOPC) bilayer is studied using united atom molecular dynamics (MD) simulations. Dynamics and transport properties of the peptide and the phospholipid bilayer are investigated. The lateral diffusion of DOPC is in the order of 10(-8) cm(2) s(-1), which is in agreement with the experimental results. The order parameter and density profile for phospholipid molecules in the bilayer are calculated. The secondary structure of amylin peptide shows that the amino acids in two terminals are structureless and two α-helical segments in the peptide are connected through an unstructured link. This structure is similar to the experimental structure in the membrane-mimicking media. Free energy calculations of the Ile26 → Pro mutation in the amylin peptide are performed in the bilayer and in aqueous solution using molecular dynamics simulations and a thermodynamic cycle. It is shown that in the mutated peptide in aqueous solution, the α-helix structure changes to a 5-helix, whereas this configuration is preserved in the bilayer environment. It is interesting that the accessible surface area increases for hydrophobic residues in the bilayer and for hydrophilic residues in aqueous solution as the coupling parameter changes from 0 to 1. These results are significant to understanding the aggregation mechanism of human amylin monomers in membranes to the dimers, trimers, oligomers, and fibrils associated with the type 2 diabetes at the atomic level.

Comparative structure-function characterization of the saposin-like domains from potato, barley, cardoon and Arabidopsis aspartic proteases.

PubMed

Bryksa, Brian C; Grahame, Douglas A; Yada, Rickey Y

2017-05-01

The present study characterized the aspartic protease saposin-like domains of four plant species, Solanum tuberosum (potato), Hordeum vulgare L. (barley), Cynara cardunculus L. (cardoon; artichoke thistle) and Arabidopsis thaliana, in terms of bilayer disruption and fusion, and structure pH-dependence. Comparison of the recombinant saposin-like domains revealed that each induced leakage of bilayer vesicles composed of a simple phospholipid mixture with relative rates Arabidopsis>barley>cardoon>potato. When compared for leakage of bilayer composed of a vacuole-like phospholipid mixture, leakage was approximately five times higher for potato saposin-like domain compared to the others. In terms of fusogenic activity, distinctions between particle size profiles were noted among the four proteins, particularly for potato saposin-like domain. Bilayer fusion assays in reducing conditions resulted in altered fusion profiles except in the case of cardoon saposin-like domain which was virtually unchanged. Secondary structure profiles were similar across all four proteins under different pH conditions, although cardoon saposin-like domain appeared to have higher overall helix structure. Furthermore, increases in Trp emission upon protein-bilayer interactions suggested that protein structure rearrangements equilibrated with half-times ranging from 52 to 120s, with cardoon saposin-like domain significantly slower than the other three species. Overall, the present findings serve as a foundation for future studies seeking to delineate protein structural features and motifs in protein-bilayer interactions based upon variability in plant aspartic protease saposin-like domain structures. Copyright © 2017 Elsevier B.V. All rights reserved.

Insight into the Properties of Cardiolipin Containing Bilayers from Molecular Dynamics Simulations, Using a Hybrid All-Atom/United-Atom Force Field.

PubMed

Aguayo, Daniel; González-Nilo, Fernando D; Chipot, Christophe

2012-05-08

Simulation of three models of cardiolipin (CL) containing membranes using a new set of parameters for tetramyristoyl and tetraoleoyl CLs has been developed in the framework of the united-atom CHARMM27-UA and the all-atom CHARMM36 force fields with the aim of performing molecular dynamics (MD) simulations of cardiolipin-containing mixed-lipid membranes. The new parameters use a hybrid representation of all-atom head groups in conjunction with implicit-hydrogen united-atom (UA) to describe the oleoyl and myristoyl chains of the CLs, in lieu of the fully atomistic description, thereby allowing longer simulations to be undertaken. The physicochemical properties of the bilayers were determined and compared with previously reported data. Furthermore, using tetramyristoyl CL mixed with POPG and POPE lipids, a mitochondrial membrane was simulated. The results presented here show the different behavior of the bilayers as a result of the lipid composition, where the length of the acyl chain and the conformation of the headgroup can be associated with the mitochondrial membrane properties. The new hybrid CL parameters prove to be well suited for the simulation of the molecular structure of CL-containing bilayers and can be extended to other lipid bilayers composed of CLs with different acyl chains or alternate head groups.

Electrochemical and PM-IRRAS Studies of the Effect of Cholesterol on the Structure of a DMPC Bilayer Supported at an Au (111) Electrode Surface, Part 1: Properties of the Acyl Chains

PubMed Central

Bin, Xiaomin; Horswell, Sarah L.; Lipkowski, Jacek

2005-01-01

Charge density measurements and polarization modulation infrared reflection absorption spectroscopy were employed to investigate the spreading of small unilamellar vesicles of a dimyristoylphosphatidylcholine (DMPC)/cholesterol (7:3 molar ratio) mixture onto an Au (111) electrode surface. The electrochemical experiments demonstrated that vesicles fuse and spread onto the Au (111) electrode surface, forming a bilayer, at rational potentials −0.4 V < (E − Epzc) < 0.4 V or field strength <6×107 V m−1. Polarization modulation infrared reflection absorption spectroscopy experiments provided information concerning the conformation and orientation of the acyl chains of DMPC molecules. Deuterated DMPC was used to subtract the contribution of C-H stretching bands of cholesterol and of the polar head region of DMPC from spectra in the C-H stretching region. The absorption spectra of the C-H stretch bands in the acyl chains were determined in this way. The properties of the DMPC/cholesterol bilayer have been compared with the properties of a pure DMPC bilayer. The presence of 30% cholesterol gives a thicker and more fluid bilayer characterized by a lower capacity and lower tilt angle of the acyl chains. PMID:15849259

Finite element analysis of the cyclic indentation of bilayer enamel

NASA Astrophysics Data System (ADS)

Jia, Yunfei; Xuan, Fu-zhen; Chen, Xiaoping; Yang, Fuqian

2014-04-01

Tooth enamel is often subjected to repeated contact and often experiences contact deformation in daily life. The mechanical strength of the enamel determines the biofunctionality of the tooth. Considering the variation of the rod arrangement in outer and inner enamel, we approximate enamel as a bilayer structure and perform finite element analysis of the cyclic indentation of the bilayer structure, to mimic the repeated contact of enamel during mastication. The dynamic deformation behaviour of both the inner enamel and the bilayer enamel is examined. The material parameters of the inner and outer enamel used in the analysis are obtained by fitting the finite element results with the experimental nanoindentation results. The penetration depth per cycle at the quasi-steady state is used to describe the depth propagation speed, which exhibits a two-stage power-law dependence on the maximum indentation load and the amplitude of the cyclic load, respectively. The continuous penetration of the indenter reflects the propagation of the plastic zone during cyclic indentation, which is related to the energy dissipation. The outer enamel serves as a protective layer due to its great resistance to contact deformation in comparison to the inner enamel. The larger equivalent plastic strain and lower stresses in the inner enamel during cyclic indentation, as calculated from the finite element analysis, indicate better crack/fracture resistance of the inner enamel.

Comparative analysis of cobalt oxide nanoisland stability and edge structures on three related noble metal surfaces: Au(111), Pt(111) and Ag(111)

DOE PAGES

Fester, Jakob; Bajdich, Michal; Walton, Alex S.; ...

2016-09-12

Here, metal oxide nanostructures and thin films grown on metallic substrates have attracted strong attention as model catalysts and as interesting inverse catalyst systems in their own right. In this study, we investigate the role of metal support in the growth and stabilization of cobalt oxide nanostructures on the three related (111) surfaces of Au, Pt and Ag, as investigated by means of high-resolution scanning tunneling microscopy and DFT calculations. All three substrates promote the growth of crystalline CoO x (x = 1–2) islands under oxidative conditions, but we find several noteworthy differences in the occurrence and stabilization of fourmore » distinct cobalt oxide island phases: Co–O bilayers, O–Co–O trilayers, Co–O–Co–O double bilayers and O–Co–O–Co–O multilayers. Using atom-resolved images combined with analysis of defect lines in bilayer islands on Au and Pt, we furthermore unambiguously determine the edge structure. Interestingly, the island shape and abundances of edge types in bilayers change radically from mixed Co/O edge terminations on Au(111) to a predominance of Co terminated edges (~91 %) on Pt(111) which is especially interesting since the Co metal edges are expected to host the most active sites for water dissociation.« less

Role of Transbilayer Distribution of Lipid Molecules on the Structure and Protein-Lipid Interaction of an Amyloidogenic Protein on the Membrane Surface

NASA Astrophysics Data System (ADS)

Cheng, Kwan; Cheng, Sara

We used molecular dynamics simulations to examine the effects of transbilayer distribution of lipid molecules, particularly anionic lipids with negatively charged headgroups, on the structure and binding kinetics of an amyloidogenic protein on the membrane surface and subsequent protein-induced structural disruption of the membrane. Our systems consisted of a model beta-sheet rich dimeric protein absorbed on asymmetric bilayers with neutral and anionic lipids and symmetric bilayers with neutral lipids. We observed larger folding, domain aggregation, and tilt angle of the absorbed protein on the asymmetric bilayer surfaces. We also detected more focused bilayer thinning in the asymmetric bilayer due to weak lipid-protein interactions. Our results support the mechanism that the higher lipid packing in the protein-contacting lipid leaflet promotes stronger protein-protein but weaker protein-lipid interactions of an amyloidogenic protein on the membrane surface. We speculate that the observed surface-induced structural and protein-lipid interaction of our model amyloidogenic protein may play a role in the early membrane-associated amyloid cascade pathway that leads to membrane structural damage of neurons in Alzheimer's disease. NSF ACI-1531594.

Controlled bending and folding of a bilayer structure consisting of a thin stiff film and a heat shrinkable polymer sheet

NASA Astrophysics Data System (ADS)

Cui, Jianxun; Adams, John G. M.; Zhu, Yong

2018-05-01

Bending pre-designed flat sheets into three-dimensional (3D) structures is attracting much interest, as it provides a simple approach to make 3D devices. Here we report controlled bending and folding of a bilayer structure consisting of a heat shrinkable polymer sheet and a thin stiff film (not thermally responsive). Upon heating, the prestrained polymer sheet shrinks, leading to bending or folding of the bilayer. We studied the effect of relative dimensions of the two layers on the bending behavior and demonstrated the transition from longitudinal bending to transverse bending of the bilayer strip. Transverse bending was utilized to fold origami structures, including several flat letters, a crane, and a corrugated metal sheet via Miura-ori folding. We developed a method to further control the bending orientation based on bio-inspired anisotropic bending stiffness. By bending the metal foil in different orientations, several structures were obtained, including cylindrical surfaces and left-handed/right-handed helical structures.

Interaction of Impulsive Pressures of Cavitation Bubbles with Cell Membranes during Sonoporation

NASA Astrophysics Data System (ADS)

Kodama, Tetsuya; Koshiyama, Ken-ichiro; Tomita, Yukio; Suzuki, Maiko; Yano, Takeru; Fujikawa, Shigeo

2006-05-01

Ultrasound contrast agents (UCAs), are capable of enhancing non-invasive cytoplasmic molecular delivery in the presence of ultrasound. Collapse of UCAs may generate nano-scale cavitation bubbles, resulting in the transient permeabilization of the cell membrane. In the present study, we investigated the interaction of a cavitation bubble-induced shock wave with a cell membrane using acoustic theory and molecular dynamics (MD) simulation. From the theory, we obtained the shock wave propagation distance from the center of a cavitation bubble that would induce membrane damage. The MD simulation determined the relationship between the uptake of water molecules into the lipid bilayer and the shock wave. The interaction of the shock wave induced a structural change of the bilayer and subsequently increased the fluidity of each molecule. These changes in the bilayer due to shock waves may be an important factor in the use of UCAs to produce the transient membrane permeability during sonoporation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Armstrong, Clare L; Barrett, M; Heiss, Arno

Inelastic neutron scattering was used to study the effect of 5 and 40 mol% cholesterol on the lateral nanoscale dynamics of phospholipid membranes. By measuring the excitation spectrum at several lateral q || values (up to q || = 3 1), complete dispersion curves were determined of gel, fluid and liquid-ordered phase bilayers. The inclusion of cholesterol had a distinct effect on the collective dynamics of the bilayer s hydrocarbon chains; specifically, we observed a pronounced stiffening of the membranes on the nanometer length scale in both gel and fluid bilayers, even though they were experiencing a higher degree ofmore » molecular disorder. Also, for the first time we determined the nanoscale dynamics in the high-cholesterol liquid-ordered phase of bilayers containing cholesterol. Namely, this phase appears to be softer than fluid bilayers, but better ordered than bilayers in the gel phase.« less

Determination of a refractive index and an extinction coefficient of standard production of CVD-graphene.

PubMed

Ochoa-Martínez, Efraín; Gabás, Mercedes; Barrutia, Laura; Pesquera, Amaia; Centeno, Alba; Palanco, Santiago; Zurutuza, Amaia; Algora, Carlos

2015-01-28

The refractive index and extinction coefficient of chemical vapour deposition grown graphene are determined by ellipsometry analysis. Graphene films were grown on copper substrates and transferred as both monolayers and bilayers onto SiO2/Si substrates by using standard manufacturing procedures. The chemical nature and thickness of residual debris formed after the transfer process were elucidated using photoelectron spectroscopy. The real layered structure so deduced has been used instead of the nominal one as the input in the ellipsometry analysis of monolayer and bilayer graphene, transferred onto both native and thermal silicon oxide. The effect of these contamination layers on the optical properties of the stacked structure is noticeable both in the visible and the ultraviolet spectral regions, thus masking the graphene optical response. Finally, the use of heat treatment under a nitrogen atmosphere of the graphene-based stacked structures, as a method to reduce the water content of the sample, and its effect on the optical response of both graphene and the residual debris layer are presented. The Lorentz-Drude model proposed for the optical response of graphene fits fairly well the experimental ellipsometric data for all the analysed graphene-based stacked structures.

Molecular structure of the dioctadecyldimethylammonium bromide (DODAB) bilayer.

PubMed

Jamróz, Dorota; Kepczynski, Mariusz; Nowakowska, Maria

2010-10-05

Dioctadecyldimethylammonium bromide (DODAB) is a double-chained quaternary ammonium surfactant that assembles in water into bilayer structures. This letter reports the molecular dynamics (MD) computer simulations of the DODAB bilayer at 25 °C. The simulations show that the surfactant membrane arranges spontaneously into the rippled phase (P(β)(')) at that temperature. The ordering within the chain fragment closest to the hydrophilic head (carbon atoms 1-5) is relatively low. It grows significantly for the carbon atoms located in the center of the membrane (atoms 6-17). The C6-C17 chain fragments are well aligned and tilted by ca. 15° with respect to the bilayer normal.

A simple analytical thermo-mechanical model for liquid crystal elastomer bilayer structures

NASA Astrophysics Data System (ADS)

Cui, Yun; Wang, Chengjun; Sim, Kyoseung; Chen, Jin; Li, Yuhang; Xing, Yufeng; Yu, Cunjiang; Song, Jizhou

2018-02-01

The bilayer structure consisting of thermal-responsive liquid crystal elastomers (LCEs) and other polymer materials with stretchable heaters has attracted much attention in applications of soft actuators and soft robots due to its ability to generate large deformations when subjected to heat stimuli. A simple analytical thermo-mechanical model, accounting for the non-uniform feature of the temperature/strain distribution along the thickness direction, is established for this type of bilayer structure. The analytical predictions of the temperature and bending curvature radius agree well with finite element analysis and experiments. The influences of the LCE thickness and the heat generation power on the bending deformation of the bilayer structure are fully investigated. It is shown that a thinner LCE layer and a higher heat generation power could yield more bending deformation. These results may help the design of soft actuators and soft robots involving thermal responsive LCEs.

Structure of Sphingomyelin Bilayers: A Simulation Study

PubMed Central

Chiu, S. W.; Vasudevan, S.; Jakobsson, Eric; Mashl, R. Jay; Scott, H. Larry

2003-01-01

We have carried out a molecular dynamics simulation of a hydrated 18:0 sphingomyelin lipid bilayer. The bilayer contained 1600 sphingomyelin (SM) molecules, and 50,592 water molecules. After construction and initial equilibration, the simulation was run for 3.8 ns at a constant temperature of 50°C and a constant pressure of 1 atm. We present properties of the bilayer calculated from the simulation, and compare with experimental data and with properties of dipalmitoyl phosphatidylcholine (DPPC) bilayers. The SM bilayers are significantly more ordered and compact than DPPC bilayers at the same temperature. SM bilayers also exhibit significant intramolecular hydrogen bonding between phosphate ester oxygen and hydroxyl hydrogen atoms. This results in a decreased hydration in the polar region of the SM bilayer compared with DPPC. Since our simulation system is very large we have calculated the power spectrum of bilayer undulation and peristaltic modes, and we compare these data with similar calculations for DPPC bilayers. We find that the SM bilayer has significantly larger bending modulus and area compressibility compared to DPPC. PMID:14645055

Coupling neutron reflectivity with cell-free protein synthesis to probe membrane protein structure in supported bilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soranzo, Thomas; Martin, Donald K.; Lenormand, Jean -Luc

Here, the structure of the p7 viroporin, an oligomeric membrane protein ion channel involved in the assembly and release of the hepatitis C virus, was determined from proteins expressed and inserted directly into supported model lipid membranes using cell-free protein expression. Cell-free protein expression allowed (i) high protein concentration in the membrane, (ii) control of the protein’s isotopic constitution, and (iii) control over the lipid environment available to the protein. Here, we used cell-free protein synthesis to directly incorporate the hepatitis C virus (HCV) p7 protein into supported lipid bilayers formed from physiologically relevant lipids (POPC or asolectin) for bothmore » direct structural measurements using neutron reflectivity (NR) and conductance measurements using electrical impedance spectroscopy (EIS). We report that HCV p7 from genotype 1a strain H77 adopts a conical shape within lipid bilayers and forms a viroporin upon oligomerization, confirmed by EIS conductance measurements. This combination of techniques represents a novel approach to the study of membrane proteins and, through the use of selective deuteration of particular amino acids to enhance neutron scattering contrast, has the promise to become a powerful tool for characterizing the protein conformation in physiologically relevant environments and for the development of biosensor applications.« less

Coupling neutron reflectivity with cell-free protein synthesis to probe membrane protein structure in supported bilayers

DOE PAGES

Soranzo, Thomas; Martin, Donald K.; Lenormand, Jean -Luc; ...

2017-06-13

Here, the structure of the p7 viroporin, an oligomeric membrane protein ion channel involved in the assembly and release of the hepatitis C virus, was determined from proteins expressed and inserted directly into supported model lipid membranes using cell-free protein expression. Cell-free protein expression allowed (i) high protein concentration in the membrane, (ii) control of the protein’s isotopic constitution, and (iii) control over the lipid environment available to the protein. Here, we used cell-free protein synthesis to directly incorporate the hepatitis C virus (HCV) p7 protein into supported lipid bilayers formed from physiologically relevant lipids (POPC or asolectin) for bothmore » direct structural measurements using neutron reflectivity (NR) and conductance measurements using electrical impedance spectroscopy (EIS). We report that HCV p7 from genotype 1a strain H77 adopts a conical shape within lipid bilayers and forms a viroporin upon oligomerization, confirmed by EIS conductance measurements. This combination of techniques represents a novel approach to the study of membrane proteins and, through the use of selective deuteration of particular amino acids to enhance neutron scattering contrast, has the promise to become a powerful tool for characterizing the protein conformation in physiologically relevant environments and for the development of biosensor applications.« less

Linking lipid architecture to bilayer structure and mechanics using self-consistent field modelling.

PubMed

Pera, H; Kleijn, J M; Leermakers, F A M

2014-02-14

To understand how lipid architecture determines the lipid bilayer structure and its mechanics, we implement a molecularly detailed model that uses the self-consistent field theory. This numerical model accurately predicts parameters such as Helfrichs mean and Gaussian bending modulus kc and k̄ and the preferred monolayer curvature J(0)(m), and also delivers structural membrane properties like the core thickness, and head group position and orientation. We studied how these mechanical parameters vary with system variations, such as lipid tail length, membrane composition, and those parameters that control the lipid tail and head group solvent quality. For the membrane composition, negatively charged phosphatidylglycerol (PG) or zwitterionic, phosphatidylcholine (PC), and -ethanolamine (PE) lipids were used. In line with experimental findings, we find that the values of kc and the area compression modulus kA are always positive. They respond similarly to parameters that affect the core thickness, but differently to parameters that affect the head group properties. We found that the trends for k̄ and J(0)(m) can be rationalised by the concept of Israelachivili's surfactant packing parameter, and that both k̄ and J(0)(m) change sign with relevant parameter changes. Although typically k̄ < 0, membranes can form stable cubic phases when the Gaussian bending modulus becomes positive, which occurs with membranes composed of PC lipids with long tails. Similarly, negative monolayer curvatures appear when a small head group such as PE is combined with long lipid tails, which hints towards the stability of inverse hexagonal phases at the cost of the bilayer topology. To prevent the destabilisation of bilayers, PG lipids can be mixed into these PC or PE lipid membranes. Progressive loading of bilayers with PG lipids lead to highly charged membranes, resulting in J(0)(m) > 0, especially at low ionic strengths. We anticipate that these changes lead to unstable membranes as these become vulnerable to pore formation or disintegration into lipid disks.

A Neutron View of Proteins in Lipid Bilayers

NASA Astrophysics Data System (ADS)

White, Stephen

2012-02-01

Despite the growing number of atomic-resolution membrane protein structures, direct structural information about proteins in their native membrane environment is scarce. This problem is particularly relevant in the case of the highly-charged S1-S4 voltage- sensing domains responsible for nerve impulses, where interactions with the lipid bilayer are critical for the function of voltage-activated potassium channels. We have used neutron diffraction, solid-state nuclear magnetic resonance spectroscopy, and molecular dynamics simulations to investigate the structure and hydration of bilayer membranes containing S1-S4 voltage-sensing domains. Our results show that voltage sensors adopt transmembrane orientations, cause a modest reshaping of the surrounding lipid bilayer, and that water molecules intimately interact with the protein within the membrane. These structural findings reveal that voltage sensors have evolved to interact with the lipid membrane while keeping the energetic and structural perturbations to a minimum, and that water penetrates into the membrane to hydrate charged residues and shape the transmembrane electric field.

Structural refinement of vitreous silica bilayers

NASA Astrophysics Data System (ADS)

Sadjadi, Mahdi; Wilson, Mark; Thorpe, M. F.

The importance of glasses resides not only in their applications but in fundamental questions that they put forth. The continuous random network model can successfully describe the glass structure, but determining details, like ring statistics, has always been difficult using only diffraction data. But recent atomic images of 2D vitreous silica bilayers can offer valuable new insights which are hard to be observed directly in 3D silica models/experiments (for references see). However, the experimental results are prone to uncertainty in atomic positions, systematic errors, and being finite. We employ special boundary conditions developed for such networks to refine the experimental structures. We show the best structure can be found by using various potentials to maximize information gained from the experimental samples. We find a range of densities, the so-called flexibility window, in which tetrahedra are perfect. We compare results from simulations using harmonic potentials, MD with atomic polarizabilities included and DFT. We should thank David Drabold and Bishal Bhattarai for useful discussions. Support through NSF Grant # DMS 1564468 is gratefully acknowledged.

Electronic and Optical Properties of Twisted Bilayer Graphene

NASA Astrophysics Data System (ADS)

Huang, Shengqiang

The ability to isolate single atomic layers of van der Waals materials has led to renewed interest in the electronic and optical properties of these materials as they can be fundamentally different at the monolayer limit. Moreover, these 2D crystals can be assembled together layer by layer, with controllable sequence and orientation, to form artificial materials that exhibit new features that are not found in monolayers nor bulk. Twisted bilayer graphene is one such prototype system formed by two monolayer graphene layers placed on top of each other with a twist angle between their lattices, whose electronic band structure depends on the twist angle. This thesis presents the efforts to explore the electronic and optical properties of twisted bilayer graphene by Raman spectroscopy and scanning tunneling microscopy measurements. We first synthesize twisted bilayer graphene with various twist angles via chemical vapor deposition. Using a combination of scanning tunneling microscopy and Raman spectroscopy, the twist angles are determined. The strength of the Raman G peak is sensitive to the electronic band structure of twisted bilayer graphene and therefore we use this peak to monitor changes upon doping. Our results demonstrate the ability to modify the electronic and optical properties of twisted bilayer graphene with doping. We also fabricate twisted bilayer graphene by controllable stacking of two graphene monolayers with a dry transfer technique. For twist angles smaller than one degree, many body interactions play an important role. It requires eight electrons per moire unit cell to fill up each band instead of four electrons in the case of a larger twist angle. For twist angles smaller than 0.4 degree, a network of domain walls separating AB and BA stacking regions forms, which are predicted to host topologically protected helical states. Using scanning tunneling microscopy and spectroscopy, these states are confirmed to appear on the domain walls when inversion symmetry is broken with an external electric field. We observe a double-line profile of these states on the domain walls, only occurring when the AB and BA regions are gaped. These states give rise to channels that could transport charge in a dissipationless manner making twisted bilayer graphene a promising platform to realize controllable topological networks for future applications.

Behavior of Bilayer Leaflets in Asymmetric Model Membranes: Atomistic Simulation Studies

DOE PAGES

Tian, Jianhui; Nickels, Jonathan; Katsaras, John; ...

2016-04-27

Spatial organization within lipid bilayers is an important feature for a range of biological processes. Leaflet compositional asymmetry and lateral lipid organization are just two of the ways in which membrane structure appears to be more complex than initially postulated by the fluid mosaic model. This raises the question of how the phase behavior in one bilayer leaflet may affect the apposing leaflet and how one begins to construct asymmetric model systems to investigate these interleaflet interactions. In this paper, we report on all-atom molecular dynamics simulations (a total of 4.1 μs) of symmetric and asymmetric bilayer systems composed ofmore » liquid-ordered (Lo) or liquid-disordered (Ld) leaflets, based on the nanodomain-forming POPC/DSPC/cholesterol system. We begin by analyzing an asymmetric bilayer with leaflets derived from simulations of symmetric Lo and Ld bilayers. In this system, we observe that the properties of the Lo and Ld leaflets are similar to those of the Lo and Ld leaflets in corresponding symmetric systems. However, it is not obvious that mixing the equilibrium structures of their symmetric counterparts is the most appropriate way to construct asymmetric bilayers nor that these structures will manifest interleaflet couplings that lead to domain registry/antiregistry. We therefore constructed and simulated four additional asymmetric bilayer systems by systematically adding or removing lipids in the Ld leaflet to mimic potential density fluctuations. We find that the number of lipids in the Ld leaflet affects its own properties, as well as those of the apposing Lo leaflet. Collectively, the simulations reveal the presence of weak acyl chain interdigitation across bilayer leaflets, suggesting that interdigitation alone does not contribute significantly to the interleaflet coupling in nonphase-separated bilayers of this chemical composition. Finally, however, the properties of both leaflets appear to be sensitive to changes in in-plane lipid packing, possibly providing a mechanism for interleaflet coupling by modulating local density and/or curvature fluctuations.« less

Substrate Efflux Propensity Is the Key Determinant of Ca2+-independent Phospholipase A-β (iPLAβ)-mediated Glycerophospholipid Hydrolysis*

PubMed Central

Batchu, Krishna Chaithanya; Hokynar, Kati; Jeltsch, Michael; Mattonet, Kenny; Somerharju, Pentti

2015-01-01

The A-type phospholipases (PLAs) are key players in glycerophospholipid (GPL) homeostasis and in mammalian cells; Ca2+-independent PLA-β (iPLAβ) in particular has been implicated in this essential process. However, the regulation of this enzyme, which is necessary to avoid futile competition between synthesis and degradation, is not understood. Recently, we provided evidence that the efflux of the substrate molecules from the bilayer is the rate-limiting step in the hydrolysis of GPLs by some secretory (nonhomeostatic) PLAs. To study whether this is the case with iPLAβ as well, a mass spectrometric assay was employed to determine the rate of hydrolysis of multiple saturated and unsaturated GPL species in parallel using micelles or vesicle bilayers as the macrosubstrate. With micelles, the hydrolysis decreased with increasing acyl chain length independent of unsaturation, and modest discrimination between acyl positional isomers was observed, presumably due to the differences in the structure of the sn-1 and sn-2 acyl-binding sites of the protein. In striking contrast, no significant discrimination between positional isomers was observed with bilayers, and the rate of hydrolysis decreased with the acyl chain length logarithmically and far more than with micelles. These data provide compelling evidence that efflux of the substrate molecule from the bilayer, which also decreases monotonously with acyl chain length, is the rate-determining step in iPLAβ-mediated hydrolysis of GPLs in membranes. This finding is intriguing as it may help to understand how homeostatic PLAs are regulated and how degradation and biosynthesis are coordinated. PMID:25713085

Transport methods for probing the barrier domain of lipid bilayer membranes.

PubMed Central

Xiang, T X; Chen, X; Anderson, B D

1992-01-01

Two experimental techniques have been utilized to explore the barrier properties of lecithin/decane bilayer membranes with the aim of determining the contributions of various domains within the bilayer to the overall barrier. The thickness of lecithin/decane bilayers was systematically varied by modulating the chemical potential of decane in the annulus surrounding the bilayer using different mole fractions of squalene in decane. The dependence of permeability of a model permeant (acetamide) on the thickness of the solvent-filled region of the bilayer was assessed in these bilayers to determine the contribution of this region to the overall barrier. The flux of acetamide was found to vary linearly with bilayer area with Pm = (2.9 +/- 0.3) x 10(-4) cm s-1, after correcting for diffusion through unstirred water layers. The ratio between the overall membrane permeability coefficient and that calculated for diffusion through the hydrocarbon core in membranes having maximum thickness was 0.24, suggesting that the solvent domain contributes only slightly to the overall barrier properties. Consistent with these results, the permeability of acetamide was found to be independent of bilayer thickness. The relative contributions of the bilayer interface and ordered hydrocarbon regions to the transport barrier may be evaluated qualitatively by exploring the effective chemical nature of the barrier microenvironment. This may be probed by comparing functional group contributions to transport with those obtained for partitioning between water and various model bulk solvents ranging in polarity or hydrogen-bonding potential. A novel approach is described for obtaining group contributions to transport using ionizable permeants and pH adjustment. Using this approach, bilayer permeability coefficients of p-toluic acid and p-hydroxymethyl benzoic acid were determined to be 1.1 +/- 0.2 cm s-1 and (1.6 +/- 0.4) x 10(-3) cm s-1, respectively. From these values, the -OH group contribution to bilayer transport [delta(delta G0-OH)] was found to be 3.9 kcal/mol. This result suggests that the barrier region of the bilayer does not resemble the hydrogen-bonding environment found in octanol, but is somewhat less selective (more polar) than a hydrocarbon solvent. PMID:1420875

Amphiphilic interactions of ionic liquids with lipid biomembranes: a molecular simulation study.

PubMed

Yoo, Brian; Shah, Jindal K; Zhu, Yingxi; Maginn, Edward J

2014-11-21

Current bottlenecks in the large-scale commercial use of many ionic liquids (ILs) include their high costs, low biodegradability, and often unknown toxicities. As a proactive effort to better understand the molecular mechanisms of ionic liquid toxicities, the work herein presents a comprehensive molecular simulation study on the interactions of 1-n-alkyl-3-methylimidazolium-based ILs with a phosphatidylcholine (PC) lipid bilayer. We explore the effects of increasing alkyl chain length (n = 4, 8, and 12) in the cation and anion hydrophobicity on the interactions with the lipid bilayer. Bulk atomistic molecular dynamics (MD) simulations performed at millimolar (mM) IL concentrations show spontaneous insertion of cations into the lipid bilayer regardless of the alkyl chain length and a favorable orientational preference once a cation is inserted. Cations also exhibit the ability to "flip" inside the lipid bilayer (as is common for amphiphiles) if partially inserted with an unfavorable orientation. Moreover, structural analysis of the lipid bilayer show that cationic insertion induces roughening of the bilayer surface, which may be a precursor to bilayer disruption. To overcome the limitation in the timescale of our simulations, free energies for a single IL cation and anion insertion have been determined based on potential of mean force calculations. These results show a decrease in free energy in response to both short and long alkyl chain IL cation insertion, and likewise for a single hydrophobic anion insertion, but an increase in free energy for the insertion of a hydrophilic chloride anion. Both bulk MD simulations and free energy calculations suggest that toxicity mechanisms toward biological systems are likely caused by ILs behaving as ionic surfactants. [Yoo et al., Soft Matter, 2014].

Phase transition of a DPPC bilayer induced by an external surface pressure: from bilayer to monolayer behavior. a molecular dynamics simulation study.

PubMed

López Cascales, J J; Otero, T F; Fernandez Romero, A J; Camacho, L

2006-06-20

Understanding the lipid phase transition of lipid bilayers is of great interest from biophysical, physicochemical, and technological points of view. With the aim of elucidating the structural changes that take place in a DPPC phospholipid bilayer induced by an external isotropic surface pressure, five computer simulations were carried out in a range from 0.1 to 40 mN/m. Molecular dynamics simulations provided insight into the structural changes that took place in the lipid structure. It was seen that low pressures ranging from 0.1 to 1 mN/m had hardly any effect on the structure, electrical properties, or hydration of the lipid bilayer. However, for pressures above 40 mN/m, there was a sharp change in the lipid-lipid interactions, hydrocarbon lipid fluidity, and electrostatic potential, corresponding to the mesomorphic transition from a liquid crystalline state (L(alpha)) to its gel state (P'(beta)). The head lipid orientation remained almost unaltered, parallel to the lipid layer, as the surface pressure was increased, although a noticeable change in its angular distribution function was evident with the phase transition.

Membrane architectures for ion-channel switch-based electrochemical biosensors

DOEpatents

Sansinena, Jose-Maria; Redondo, Antonio; Swanson, Basil I.; Yee, Chanel Kitmon; Sapuri/Butti, Annapoorna R.; Parikh, Atul N.; Yang, Calvin

2008-10-28

The present invention is directed to a process of forming a bilayer lipid membrane structure by depositing an organic layer having a defined surface area onto an electrically conductive substrate, removing portions of said organic layer upon said electrically conductive substrate whereby selected portions of said organic layer are removed to form defined voids within said defined surface area of said organic layer and defined islands of organic layer upon said electrically conductive substrate, and, depositing a bilayer lipid membrane over the defined voids and defined islands of organic layer upon said substrate whereby aqueous reservoirs are formed between said electrically conductive substrate and said bilayer lipid membrane, said bilayer lipid membrane characterized as spanning across the defined voids between said defined islands. A lipid membrane structure is also described together with an array of such lipid membrane structure.

Lipopolysaccharide Membrane Building and Simulation

PubMed Central

Jo, Sunhwan; Wu, Emilia L.; Stuhlsatz, Danielle; Klauda, Jeffery B.; Widmalm, Göran; Im, Wonpil

2015-01-01

Summary While membrane simulations are widely employed to study the structure and dynamics of various lipid bilayers and membrane proteins in the bilayers, simulations of lipopolysaccharides (LPS) in membrane environments have been limited due to its structural complexity, difficulties in building LPS-membrane systems, and lack of appropriate molecular force field. In this work, as a first step to extend CHARMM-GUI Membrane Builder to incorporate LPS molecules and to explore their structures and dynamics in membrane environments using molecular dynamics simulations, we describe step-by-step procedures to build LPS bilayer systems using CHARMM and the recently developed CHARMM carbohydrate and lipid force fields. Such procedures are illustrated by building various bilayers of Escherichia coli O6 LPS and their preliminary simulation results are given in terms of per-LPS area and density distributions of various components along the membrane normal. PMID:25753722

Theoretical investigation of structural and optical properties of semi-fluorinated bilayer graphene

NASA Astrophysics Data System (ADS)

Xiao-Jiao, San; Bai, Han; Jing-Geng, Zhao

2016-03-01

We have studied the structural and optical properties of semi-fluorinated bilayer graphene using density functional theory. When the interlayer distance is 1.62 Å, the two graphene layers in AA stacking can form strong chemical bonds. Under an in-plane stress of 6.8 GPa, this semi-fluorinated bilayer graphene becomes the energy minimum. Our calculations indicate that the semi-fluorinated bilayer graphene with the AA stacking sequence and rectangular fluorinated configuration is a nonmagnetic semiconductor (direct gap of 3.46 eV). The electronic behavior at the vicinity of the Fermi level is mainly contributed by the p electrons of carbon atoms forming C=C double bonds. We compare the optical properties of the semi-fluorinated bilayer graphene with those of bilayer graphene stacked in the AA sequence and find that the semi-fluorinated bilayer graphene is anisotropic for the polarization vector on the basal plane of graphene and a red shift occurs in the [010] polarization, which makes the peak at the low-frequency region located within visible light. This investigation is useful to design polarization-dependence optoelectronic devices. Project supported by the Program of Educational Commission of Heilongjiang Province, China (Grant No. 12541131).

Structure formation in binary mixtures of lipids and detergents: self-assembly and vesicle division.

PubMed

Noguchi, Hiroshi

2013-01-14

Self-assembly dynamics in binary surfactant mixtures and structure changes of lipid vesicles induced by detergent solution are studied using coarse-grained molecular simulations. Disk-shaped micelles, the bicelles, are stabilized by detergents surrounding the rim of a bilayer disk of lipids. The self-assembled bicelles are considerably smaller than bicelles formed from vesicle rupture, and their size is determined by the concentrations of lipids and detergents and the interactions between the two species. The detergent-adsorption induces spontaneous curvature of the vesicle bilayer and results in vesicle division into two vesicles or vesicle rupture into worm-like micelles. The division occurs mainly via the inverse pathway of the modified stalk model. For large spontaneous curvature of the monolayers of the detergents, a pore is often opened, thereby leading to vesicle division or worm-like micelle formation.

Ultra-high vacuum surface analysis study of rhodopsin incorporation into supported lipid bilayers.

PubMed

Michel, Roger; Subramaniam, Varuni; McArthur, Sally L; Bondurant, Bruce; D'Ambruoso, Gemma D; Hall, Henry K; Brown, Michael F; Ross, Eric E; Saavedra, S Scott; Castner, David G

2008-05-06

Planar supported lipid bilayers that are stable under ambient atmospheric and ultra-high-vacuum conditions were prepared by cross-linking polymerization of bis-sorbylphosphatidylcholine (bis-SorbPC). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were employed to investigate bilayers that were cross-linked using either redox-initiated radical polymerization or ultraviolet photopolymerization. The redox method yields a more structurally intact bilayer; however, the UV method is more compatible with incorporation of transmembrane proteins. UV polymerization was therefore used to prepare cross-linked bilayers with incorporated bovine rhodopsin, a light-activated, G-protein-coupled receptor (GPCR). A previous study (Subramaniam, V.; Alves, I. D.; Salgado, G. F. J.; Lau, P. W.; Wysocki, R. J.; Salamon, Z.; Tollin, G.; Hruby, V. J.; Brown, M. F.; Saavedra, S. S. J. Am. Chem. Soc. 2005, 127, 5320-5321) showed that rhodopsin retains photoactivity after incorporation into UV-polymerized bis-SorbPC, but did not address how the protein is associated with the bilayer. In this study, we show that rhodopsin is retained in supported bilayers of poly(bis-SorbPC) under ultra-high-vacuum conditions, on the basis of the increase in the XPS nitrogen concentration and the presence of characteristic amino acid peaks in the ToF-SIMS data. Angle-resolved XPS data show that the protein is inserted into the bilayer, rather than adsorbed on the bilayer surface. This is the first study to demonstrate the use of ultra-high-vacuum techniques for structural studies of supported proteolipid bilayers.

Rational Design of ZnO:H/ZnO Bilayer Structure for High-Performance Thin-Film Transistors.

PubMed

Abliz, Ablat; Huang, Chun-Wei; Wang, Jingli; Xu, Lei; Liao, Lei; Xiao, Xiangheng; Wu, Wen-Wei; Fan, Zhiyong; Jiang, Changzhong; Li, Jinchai; Guo, Shishang; Liu, Chuansheng; Guo, Tailiang

2016-03-01

The intriguing properties of zinc oxide-based semiconductors are being extensively studied as they are attractive alternatives to current silicon-based semiconductors for applications in transparent and flexible electronics. Although they have promising properties, significant improvements on performance and electrical reliability of ZnO-based thin film transistors (TFTs) should be achieved before they can be applied widely in practical applications. This work demonstrates a rational and elegant design of TFT, composed of poly crystalline ZnO:H/ZnO bilayer structure without using other metal elements for doping. The field-effect mobility and gate bias stability of the bilayer structured devices have been improved. In this device structure, the hydrogenated ultrathin ZnO:H active layer (∼3 nm) could provide suitable carrier concentration and decrease the interface trap density, while thick pure-ZnO layer could control channel conductance. Based on this novel structure, a high field-effect mobility of 42.6 cm(2) V(-1) s(-1), a high on/off current ratio of 10(8) and a small subthreshold swing of 0.13 V dec(-1) have been achieved. Additionally, the bias stress stability of the bilayer structured devices is enhanced compared to the simple single channel layer ZnO device. These results suggest that the bilayer ZnO:H/ZnO TFTs have a great potential for low-cost thin-film electronics.

A high extinction ratio THz polarizer fabricated by double-bilayer wire grid structure

NASA Astrophysics Data System (ADS)

Lu, Bin; Wang, Haitao; Shen, Jun; Yang, Jun; Mao, Hongyan; Xia, Liangping; Zhang, Weiguo; Wang, Guodong; Peng, Xiao-Yu; Wang, Deqiang

2016-02-01

We designed a new style of broadband terahertz (THz) polarizer with double-bilayer wire grid structure by fabricating them on both sides of silicon substrate. This THz polarizer shows a high average extinction ratio of 60dB in 0.5 to 2.0 THz frequency range and the maximum of 87 dB at 1.06 THz, which is much higher than that of conventional monolayer wire grid polarizers and single-bilayer wire grid ones.

Low-voltage organic thin film transistors (OTFTs) using crosslinked polyvinyl alcohol (PVA)/neodymium oxide (Nd2O3) bilayer gate dielectrics

NASA Astrophysics Data System (ADS)

Khound, Sagarika; Sarma, Ranjit

2018-01-01

We have reported here on the design, processing and dielectric properties of pentacene-based organic thin film transitors (OTFTs) with a bilayer gate dilectrics of crosslinked PVA/Nd2O3 which enables low-voltage organic thin film operations. The dielectric characteristics of PVA/Nd2O3 bilayer films are studied by capacitance-voltage ( C- V) and current-voltage ( I- V) curves in the metal-insulator-metal (MIM) structure. We have analysed the output electrical responses and transfer characteristics of the OTFT devices to determine their performance of OTFT parameters. The mobility of 0.94 cm2/Vs, the threshold voltage of - 2.8 V, the current on-off ratio of 6.2 × 105, the subthreshold slope of 0.61 V/decade are evaluated. Low leakage current of the device is observed from current density-electric field ( J- E) curve. The structure and the morphology of the device are studied using X-ray diffraction (XRD) and atomic force microscope (AFM), respectively. The study demonstrates an effective way to realize low-voltage, high-performance OTFTs at low cost.

A Computational Approach for Modeling Neutron Scattering Data from Lipid Bilayers

DOE PAGES

Carrillo, Jan-Michael Y.; Katsaras, John; Sumpter, Bobby G.; ...

2017-01-12

Biological cell membranes are responsible for a range of structural and dynamical phenomena crucial to a cell's well-being and its associated functions. Due to the complexity of cell membranes, lipid bilayer systems are often used as biomimetic models. These systems have led to signficant insights into vital membrane phenomena such as domain formation, passive permeation and protein insertion. Experimental observations of membrane structure and dynamics are, however, limited in resolution, both spatially and temporally. Importantly, computer simulations are starting to play a more prominent role in interpreting experimental results, enabling a molecular under- standing of lipid membranes. Particularly, the synergymore » between scattering experiments and simulations offers opportunities for new discoveries in membrane physics, as the length and time scales probed by molecular dynamics (MD) simulations parallel those of experiments. We also describe a coarse-grained MD simulation approach that mimics neutron scattering data from large unilamellar lipid vesicles over a range of bilayer rigidity. Specfically, we simulate vesicle form factors and membrane thickness fluctuations determined from small angle neutron scattering (SANS) and neutron spin echo (NSE) experiments, respectively. Our simulations accurately reproduce trends from experiments and lay the groundwork for investigations of more complex membrane systems.« less

Method for obtaining structure and interactions from oriented lipid bilayers

PubMed Central

Lyatskaya, Yulia; Liu, Yufeng; Tristram-Nagle, Stephanie; Katsaras, John; Nagle, John F.

2009-01-01

Precise calculations are made of the scattering intensity I(q) from an oriented stack of lipid bilayers using a realistic model of fluctuations. The quantities of interest include the bilayer bending modulus Kc , the interbilayer interaction modulus B, and bilayer structure through the form factor F(qz). It is shown how Kc and B may be obtained from data at large qz where fluctuations dominate. Good estimates of F(qz) can be made over wide ranges of qz by using I(q) in q regions away from the peaks and for qr≠0 where details of the scattering domains play little role. Rough estimates of domain sizes can also be made from smaller qz data. Results are presented for data taken on fully hydrated, oriented DOPC bilayers in the Lα phase. These results illustrate the advantages of oriented samples compared to powder samples. PMID:11304287

Entanglement entropy and entanglement spectrum of Bi_1-xSb_x (111) bilayers.

PubMed

Brzezińska, Marta; Bieniek, Maciej; Woźniak, Tomasz; Potasz, Paweł; Wójs, Arkadiusz

2018-02-14

We study topological properties of Bi$_{1-x}$Sb$_{x}$ bilayers in the (111) plane using entanglement measures. Electronic structures are investigated within multi-orbital tight-binding model and structural stability is confirmed through first-principles calculations. Topologically non-trivial nature of bismuth bilayer is proved by the presence of spectral flow in the entanglement spectrum. We consider topological phase transitions driven by a composition change x, an applied external electric field in Bi bilayer and strain in Sb bilayer. Composition- and strain-induced phase transitions reveal a finite discontinuity in the entanglement entropy. This quantity remains a continuous function of the electric field strength, but shows a finite discontinuity in the first derivative. We relate the difference in behavior of the entanglement entropy to the breaking of inversion symmetry in the last case. © 2018 IOP Publishing Ltd.

Entanglement entropy and entanglement spectrum of Bi1-x Sb x (1 1 1) bilayers.

PubMed

Brzezińska, Marta; Bieniek, Maciej; Woźniak, Tomasz; Potasz, Paweł; Wójs, Arkadiusz

2018-02-28

We study topological properties of Bi 1-x Sb x bilayers in the (1 1 1) plane using entanglement measures. Electronic structures are investigated within multi-orbital tight-binding model and structural stability is confirmed through first-principles calculations. The topologically non-trivial nature of the bismuth bilayer is proved by the presence of spectral flow in the entanglement spectrum. We consider topological phase transitions driven by a composition change x, an applied external electric field in Bi bilayers and strain in Sb bilayers. Composition- and strain-induced phase transitions reveal a finite discontinuity in the entanglement entropy. This quantity remains a continuous function of the electric field strength, but shows a finite discontinuity in the first derivative. We relate the difference in behavior of the entanglement entropy to the breaking of inversion symmetry in the last case.

Enhanced magnetoelectric response in 2-2 bilayer 0.50Pb(Ni1/3Nb2/3)O3-0.35PbTiO3-0.15PbZrO3/NiFe2O4 thin films

NASA Astrophysics Data System (ADS)

Ade, Ramesh; Sambasiva, V.; Kolte, Jayant; Karthik, T.; Kulkarni, Ajit R.; Venkataramani, N.

2018-03-01

In this work, room temperature magnetoelectric (ME) properties of 0.50Pb(Ni1/3Nb2/3)O3-0.35PbTiO3-0.15PbZrO3 (PNNZT)/NiFe2O4 (NFO) 2-2 bilayer thin films grown on Pt/Ti/SiO2/Si substrate, using pulsed laser deposition technique, are reported. Structural studies confirm single phase PNNZT/NFO 2-2 bilayer structure formation. PNNZT/NFO 2-2 bilayer thin film shows a maximum ME voltage coefficient (α E ) of ~0.70 V cm-1. Oe-1 at a frequency of 1 kHz. The present study reveals that PNNZT/NFO bilayer thin film can be a potential candidate for technological applications.

Molecular design and MD simulations of epitaxial superlattice of self-assembling ternary lipid bilayers

NASA Astrophysics Data System (ADS)

Chou, George; Vaughn, Mark; Cheng, K.

2011-10-01

Multicomponent lipid bilayers represent an important model system for studying cell membranes. At present, an ordered multicomponent phospholipid/cholesterol bilayer system involving charged lipid is still not available. Using a lipid superlattice (SL) model, a 13 x 15 x 15 nm^3 ternary phosphatidylcholine/phosphatidylserine/cholesterol bilayer system in water with simultaneous headgroup SL and acyl chain SL at different depths, or epitaxial SL, of the bilayer has been designed with atomistic detail. The arrangements of this epitaxial SL system were optimized by only two molecular parameters, lattice space and rotational angle of the lipids. Using atomistic MD simulations, we demonstrated the stability of the ordered structures for more than 100 ns. A positional restrained system was also used as a control. This system will provide new insights into understanding the nanodomain structures of cell membranes at the molecular level.

Enhancement of resistive switching properties in Al2O3 bilayer-based atomic switches: multilevel resistive switching

NASA Astrophysics Data System (ADS)

Vishwanath, Sujaya Kumar; Woo, Hyunsuk; Jeon, Sanghun

2018-06-01

Atomic switches are considered to be building blocks for future non-volatile data storage and internet of things. However, obtaining device structures capable of ultrahigh density data storage, high endurance, and long data retention, and more importantly, understanding the switching mechanisms are still a challenge for atomic switches. Here, we achieved improved resistive switching performance in a bilayer structure containing aluminum oxide, with an oxygen-deficient oxide as the top switching layer and stoichiometric oxide as the bottom switching layer, using atomic layer deposition. This bilayer device showed a high on/off ratio (105) with better endurance (∼2000 cycles) and longer data retention (104 s) than single-oxide layers. In addition, depending on the compliance current, the bilayer device could be operated in four different resistance states. Furthermore, the depth profiles of the hourglass-shaped conductive filament of the bilayer device was observed by conductive atomic force microscopy.

Entanglement entropy and entanglement spectrum of Bi1-x Sb x (1 1 1) bilayers

NASA Astrophysics Data System (ADS)

Brzezińska, Marta; Bieniek, Maciej; Woźniak, Tomasz; Potasz, Paweł; Wójs, Arkadiusz

2018-03-01

We study topological properties of Bi1-x Sb x bilayers in the (1 1 1) plane using entanglement measures. Electronic structures are investigated within multi-orbital tight-binding model and structural stability is confirmed through first-principles calculations. The topologically non-trivial nature of the bismuth bilayer is proved by the presence of spectral flow in the entanglement spectrum. We consider topological phase transitions driven by a composition change x, an applied external electric field in Bi bilayers and strain in Sb bilayers. Composition- and strain-induced phase transitions reveal a finite discontinuity in the entanglement entropy. This quantity remains a continuous function of the electric field strength, but shows a finite discontinuity in the first derivative. We relate the difference in behavior of the entanglement entropy to the breaking of inversion symmetry in the last case.

Topological magnetic phase in LaMnO3 (111) bilayer

NASA Astrophysics Data System (ADS)

Weng, Yakui; Huang, Xin; Yao, Yugui; Dong, Shuai

2015-11-01

Candidates for correlated topological insulators, originated from the spin-orbit coupling as well as the Hubbard-type correlation, are expected in the (111) bilayer of perovskite-structural transition-metal oxides. Based on the first-principles calculation and tight-binding model, the electronic structure of a LaMnO3 (111) bilayer sandwiched in LaScO3 barriers has been investigated. For the ideal undistorted perovskite structure, the Fermi energy of LaMnO3 (111) bilayer just stays at the Dirac point, rendering a semimetal (graphenelike) which is also a half metal [different from graphene or the previously studied LaNiO3 (111) bilayer]. The Dirac cone can be opened by the spin-orbit coupling, giving rise to nontrivial topological bands corresponding to the (quantized) anomalous Hall effect. For the realistic orthorhombic distorted lattice, the Dirac point moves with increasing Hubbard repulsion (or equivalent Jahn-Teller distortion). Finally, a Mott gap opens, establishing a phase boundary between the Mott insulator and topological magnetic insulator. Our calculation finds that the gap opened by spin-orbit coupling is much smaller in the orthorhombic distorted lattice (˜1.7 meV) than the undistorted one (˜11 meV). Therefore, to suppress the lattice distortion can be helpful to enhance the robustness of the topological phase in perovskite (111) bilayers.

Multidimensional oriented solid-state NMR experiments enable the sequential assignment of uniformly 15N labeled integral membrane proteins in magnetically aligned lipid bilayers.

PubMed

Mote, Kaustubh R; Gopinath, T; Traaseth, Nathaniel J; Kitchen, Jason; Gor'kov, Peter L; Brey, William W; Veglia, Gianluigi

2011-11-01

Oriented solid-state NMR is the most direct methodology to obtain the orientation of membrane proteins with respect to the lipid bilayer. The method consists of measuring (1)H-(15)N dipolar couplings (DC) and (15)N anisotropic chemical shifts (CSA) for membrane proteins that are uniformly aligned with respect to the membrane bilayer. A significant advantage of this approach is that tilt and azimuthal (rotational) angles of the protein domains can be directly derived from analytical expression of DC and CSA values, or, alternatively, obtained by refining protein structures using these values as harmonic restraints in simulated annealing calculations. The Achilles' heel of this approach is the lack of suitable experiments for sequential assignment of the amide resonances. In this Article, we present a new pulse sequence that integrates proton driven spin diffusion (PDSD) with sensitivity-enhanced PISEMA in a 3D experiment ([(1)H,(15)N]-SE-PISEMA-PDSD). The incorporation of 2D (15)N/(15)N spin diffusion experiments into this new 3D experiment leads to the complete and unambiguous assignment of the (15)N resonances. The feasibility of this approach is demonstrated for the membrane protein sarcolipin reconstituted in magnetically aligned lipid bicelles. Taken with low electric field probe technology, this approach will propel the determination of sequential assignment as well as structure and topology of larger integral membrane proteins in aligned lipid bilayers. © Springer Science+Business Media B.V. 2011

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fester, Jakob; Bajdich, Michal; Walton, Alex S.

Here, metal oxide nanostructures and thin films grown on metallic substrates have attracted strong attention as model catalysts and as interesting inverse catalyst systems in their own right. In this study, we investigate the role of metal support in the growth and stabilization of cobalt oxide nanostructures on the three related (111) surfaces of Au, Pt and Ag, as investigated by means of high-resolution scanning tunneling microscopy and DFT calculations. All three substrates promote the growth of crystalline CoO x (x = 1–2) islands under oxidative conditions, but we find several noteworthy differences in the occurrence and stabilization of fourmore » distinct cobalt oxide island phases: Co–O bilayers, O–Co–O trilayers, Co–O–Co–O double bilayers and O–Co–O–Co–O multilayers. Using atom-resolved images combined with analysis of defect lines in bilayer islands on Au and Pt, we furthermore unambiguously determine the edge structure. Interestingly, the island shape and abundances of edge types in bilayers change radically from mixed Co/O edge terminations on Au(111) to a predominance of Co terminated edges (~91 %) on Pt(111) which is especially interesting since the Co metal edges are expected to host the most active sites for water dissociation.« less

Direct in situ measurement of specific capacitance, monolayer tension, and bilayer tension in a droplet interface bilayer

DOE PAGES

Taylor, Graham J.; Venkatesan, Guru A.; Collier, C. Patrick; ...

2015-08-05

In this study, thickness and tension are important physical parameters of model cell membranes. However, traditional methods to measure these quantities require multiple experiments using separate equipment. This work introduces a new multi-step procedure for directly accessing in situ multiple physical properties of droplet interface bilayers (DIB), including specific capacitance (related to thickness), lipid monolayer tension in the Plateau-Gibbs border, and bilayer tension. The procedure employs a combination of mechanical manipulation of bilayer area followed by electrowetting of the capacitive interface to examine the sensitivities of bilayer capacitance to area and contact angle to voltage, respectively. These data allow formore » determining the specific capacitance of the membrane and surface tension of the lipid monolayer, which are then used to compute bilayer thickness and tension, respectively. The use of DIBs affords accurate optical imaging of the connected droplets in addition to electrical measurements of bilayer capacitance, and it allows for reversibly varying bilayer area. After validating the accuracy of the technique with diphytanoyl phosphatidylcholine (DPhPC) DIBs in hexadecane, the method is applied herein to quantify separately the effects on membrane thickness and tension caused by varying the solvent in which the DIB is formed and introducing cholesterol into the bilayer. Because the technique relies only on capacitance measurements and optical images to determine both thickness and tension, this approach is specifically well-suited for studying the effects of peptides, biomolecules, natural and synthetic nanoparticles, and other species that accumulate within membranes without altering bilayer conductance.« less

Quantifying the bending of bilayer temperature-sensitive hydrogels

NASA Astrophysics Data System (ADS)

Dong, Chenling; Chen, Bin

2017-04-01

Stimuli-responsive hydrogels can serve as manipulators, including grippers, sensors, etc., where structures can undergo significant bending. Here, a finite-deformation theory is developed to quantify the evolution of the curvature of bilayer temperature-sensitive hydrogels when subjected to a temperature change. Analysis of the theory indicates that there is an optimal thickness ratio to acquire the largest curvature in the bilayer and also suggests that the sign or the magnitude of the curvature can be significantly affected by pre-stretches or small pores in the bilayer. This study may provide important guidelines in fabricating temperature-responsive bilayers with desirable mechanical performance.

Functional liposomes and supported lipid bilayers: towards the complexity of biological archetypes.

PubMed

Berti, Debora; Caminati, Gabriella; Baglioni, Piero

2011-05-21

This perspective paper provides some illustrative examples on the interplay between information gathered on planar supported lipid bilayers (SLB) and unilamellar lipid vesicles (ULV) to get an integrated description of phenomena occurring at the nanoscale that involve locally bilayered structures. Similarities and differences are underlined and critically compared in terms of biomimetic fidelity and instrumental accessibility to structural and dynamical parameters, focusing on some recent reports that either explicitly address this comparison or introducing some studies that separately investigate the same process in SLB and lipid vesicles. Despite the structural similarity on the nanoscale, the different topology implies radically different characterization techniques that have evolved in sectorial and separated approaches. The quest for increasing levels of compositional complexity for bilayered systems should not result in a loss of structural and dynamical control: this is the central challenge of future research in this area, where the integrated approach highlighted in this contribution would enable improved levels of understanding. © The Owner Societies 2011

Thickness dependencies of structural and magnetic properties of cubic and tetragonal Heusler alloy bilayer films

NASA Astrophysics Data System (ADS)

Ranjbar, R.; Suzuki, K. Z.; Sugihara, A.; Ando, Y.; Miyazaki, T.; Mizukami, S.

2017-07-01

The thickness dependencies of the structural and magnetic properties for bilayers of cubic Co-based Heusler alloys (CCHAs: Co2FeAl (CFA), Co2FeSi (CFS), Co2MnAl (CMA), and Co2MnSi (CMS)) and D022-MnGa were investigated. Epitaxy of the B2 structure of CCHAs on a MnGa film was achieved; the smallest thickness with the B2 structure was found for 3-nm-thick CMS and CFS. The interfacial exchange coupling (Jex) was antiferromagnetic (AFM) for all of the CCHAs/MnGa bilayers except for unannealed CFA/MnGa samples. A critical thickness (tcrit) at which perpendicular magnetization appears of approximately 4-10 nm for the CMA/MnGa and CMS/MnGa bilayers was observed, whereas this thickness was 1-3 nm for the CFA/MnGa and CFS/MnGa films. The critical thickness for different CCHAs materials is discussed in terms of saturation magnetization (Ms) and the Jex .

Obesity resistance and deregulation of lipogenesis in Δ6-fatty acid desaturase (FADS2) deficiency.

PubMed

Stoffel, Wilhelm; Hammels, Ina; Jenke, Britta; Binczek, Erika; Schmidt-Soltau, Inga; Brodesser, Susanne; Odenthal, Margarete; Thevis, Mario

2014-01-01

Δ-6-fatty acid desaturase (FADS2) is the key enzyme in the biosynthesis of polyunsaturated fatty acids (PUFAs), the essential structural determinants of mammalian membrane lipid-bilayers. We developed the auxotrophic fads2(-/-) mouse mutant to assess the enigmatic role of ω3- and ω6-PUFAs in lipid homeostasis, membrane structure and function. Obesity resistance is another major phenotype of the fads2(-/-) mutant, the molecular basis of which is unknown. Phospholipidomic profiling of membrane systems of fads2(-/-)mice revealed diacylglycerol-structures, deprived of PUFAs but substituted with surrogate eicosa-5,11,14-trienoic acid. ω6-Arachidonic (AA) and ω3-docosahexaenoic acid (DHA) supplemented diets transformed fads2(-/-) into AA-fads2(-/-) and DHA-fads2(-/-) mutants. Severely altered phospholipid-bilayer structures of subcellular membranes of fads2(-/-) liver specifically interfered with maturation of transcription factor sterol-regulatory-element-binding protein, the key regulator of lipogenesis and lipid homeostasis. This study strengthens the concept that specific PUFA-substituted membrane phospholipid species are critical constituents of the structural platform operative in lipid homeostasis in normal and disease conditions.

Topological Valley Transport at Bilayer Graphene Domain Walls

DTIC Science & Technology

2015-04-22

2015. Published online 22 April 2015. 1. McCann, E. Asymmetry gap in the electronic band structure of bilayer graphene . Phys. Rev. B 74, 161403 (2006...6. Yao, W., Yang, S. A. & Niu, Q. Edge states in graphene : from gapped flat- band to gapless chiral modes. Phys. Rev. Lett. 102, 096801 (2009). 7...induced in bilayer graphene by an external electric field1–5, and such gapped bilayer graphene is predicted to be a topo- logical insulating phase

Mechanical properties of drug loaded diblock copolymer bilayers: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Grillo, Damián A.; Albano, Juan M. R.; Mocskos, Esteban E.; Facelli, Julio C.; Pickholz, Mónica; Ferraro, Marta B.

2018-06-01

In this work, we present results of coarse-grained simulations to study the encapsulation of prilocaine (PLC), both neutral and protonated, on copolymer bilayers through molecular dynamics simulations. Using a previously validated membrane model, we have simulated loaded bilayers at different drug concentrations and at low (protonated PLC) and high (neutral PLC) pH levels. We have characterized key structural parameters of the loaded bilayers in order to understand the effects of encapsulation of PLC on the bilayer structure and mechanical properties. Neutral PLC was encapsulated in the hydrophobic region leading to a thickness increase, while the protonated species partitioned between the water phase and the poly(ethylene oxide)-poly(butadiene) (PBD) interface, relaxing the PBD region and leading to a decrease in the thickness. The tangential pressures of the studied systems were calculated, and their components were decomposed in order to gain insights on their compensation. In all cases, it is observed that the loading of the membrane does not significantly decrease the stability of the bilayer, indicating that the system could be used for drug delivery.

Mechanical properties of drug loaded diblock copolymer bilayers: A molecular dynamics study.

PubMed

Grillo, Damián A; Albano, Juan M R; Mocskos, Esteban E; Facelli, Julio C; Pickholz, Mónica; Ferraro, Marta B

2018-06-07

In this work, we present results of coarse-grained simulations to study the encapsulation of prilocaine (PLC), both neutral and protonated, on copolymer bilayers through molecular dynamics simulations. Using a previously validated membrane model, we have simulated loaded bilayers at different drug concentrations and at low (protonated PLC) and high (neutral PLC) pH levels. We have characterized key structural parameters of the loaded bilayers in order to understand the effects of encapsulation of PLC on the bilayer structure and mechanical properties. Neutral PLC was encapsulated in the hydrophobic region leading to a thickness increase, while the protonated species partitioned between the water phase and the poly(ethylene oxide)-poly(butadiene) (PBD) interface, relaxing the PBD region and leading to a decrease in the thickness. The tangential pressures of the studied systems were calculated, and their components were decomposed in order to gain insights on their compensation. In all cases, it is observed that the loading of the membrane does not significantly decrease the stability of the bilayer, indicating that the system could be used for drug delivery.

Calcium and zinc differentially affect the structure of lipid membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kučerka, Norbert; Dushanov, Ermuhammad; Kholmurodov, Kholmirzo T.

Interactions of calcium (Ca 2+) and zinc (Zn 2+) cations with biomimetic membranes made of dipalmitoylphosphatidylcholine (DPPC) were studied by small angle neutron diffraction (SAND). Experiments show that the structure of these lipid bilayers is differentially affected by the two divalent cations. Initially, both Ca 2+ and Zn 2+ cause DPPC bilayers to thicken, while further increases in Ca 2+ concentration result in the bilayer thinning, eventually reverting to having the same thickness as pure DPPC. The binding of Zn 2+, on the other hand, causes the bilayers to swell to a maximum thickness, and the addition of more Znmore » 2+ does not result in a further thickening of the membrane. Agreement between our results obtained using oriented planar membranes and those from vesicular samples implies that the effect of cations on bilayer thickness is the result of electrostatic interactions, rather than geometrical constraints due to bilayer curvature. This notion is further reinforced by MD simulations. Lastly, the radial distribution functions reveal a strong interaction between Ca 2+ and the phosphate oxygens, while Zn 2+ shows a much weaker binding specificity.« less

Calcium and zinc differentially affect the structure of lipid membranes

DOE PAGES

Kučerka, Norbert; Dushanov, Ermuhammad; Kholmurodov, Kholmirzo T.; ...

2017-03-09

Interactions of calcium (Ca 2+) and zinc (Zn 2+) cations with biomimetic membranes made of dipalmitoylphosphatidylcholine (DPPC) were studied by small angle neutron diffraction (SAND). Experiments show that the structure of these lipid bilayers is differentially affected by the two divalent cations. Initially, both Ca 2+ and Zn 2+ cause DPPC bilayers to thicken, while further increases in Ca 2+ concentration result in the bilayer thinning, eventually reverting to having the same thickness as pure DPPC. The binding of Zn 2+, on the other hand, causes the bilayers to swell to a maximum thickness, and the addition of more Znmore » 2+ does not result in a further thickening of the membrane. Agreement between our results obtained using oriented planar membranes and those from vesicular samples implies that the effect of cations on bilayer thickness is the result of electrostatic interactions, rather than geometrical constraints due to bilayer curvature. This notion is further reinforced by MD simulations. Lastly, the radial distribution functions reveal a strong interaction between Ca 2+ and the phosphate oxygens, while Zn 2+ shows a much weaker binding specificity.« less

Strain and curvature induced evolution of electronic band structures in twisted graphene bilayer.

PubMed

Yan, Wei; He, Wen-Yu; Chu, Zhao-Dong; Liu, Mengxi; Meng, Lan; Dou, Rui-Fen; Zhang, Yanfeng; Liu, Zhongfan; Nie, Jia-Cai; He, Lin

2013-01-01

It is well established that strain and geometry could affect the band structure of graphene monolayer dramatically. Here we study the evolution of local electronic properties of a twisted graphene bilayer induced by a strain and a high curvature, which are found to strongly affect the local band structures of the twisted graphene bilayer. The energy difference of the two low-energy van Hove singularities decreases with increasing lattice deformation and the states condensed into well-defined pseudo-Landau levels, which mimic the quantization of massive chiral fermions in a magnetic field of about 100 T, along a graphene wrinkle. The joint effect of strain and out-of-plane distortion in the graphene wrinkle also results in a valley polarization with a significant gap. These results suggest that strained graphene bilayer could be an ideal platform to realize the high-temperature zero-field quantum valley Hall effect.

Polyunsaturated Fatty Acids in Lipid Bilayers and Tubules

NASA Astrophysics Data System (ADS)

Hirst, Linda S.; Yuan, Jing; Pramudya, Yohannes; Nguyen, Lam T.

2007-03-01

Omega-3 polyunsaturated fatty acids (PUFAs) are found in a variety of biological membranes and have been implicated with lipid raft formation and possible function, typical molecules include DHA (Docosahexanoic Acid) and AA (Alphalinoleic Acid) which have been the focus of considerable attention in recent years. We are interested in the phase behavior of these molecules in the lipid bilayer. The addition of lipid molecules with polyunsaturated chains has a clear effect on the fluidity and curvature of the membrane and we investigate the effects the addition of polyunsaturated lipids on bilayer structure and tubule formation. Self-assembled cylindrical lipid tubules have attracted considerable attention because of their interesting structures and potential technological applications. Using x-ray diffraction techniques, Atomic Force Microscopy and confocal fluorescence imaging, both symmetric and mixed chain lipids were incorporated into model membranes and the effects on bilayer structure and tubule formation investigated.

Partitioning of lysolipids, fatty acids and their mixtures in aqueous lipid bilayers: solute concentration/composition effects.

PubMed

Singh, Jasmeet; Lai, Amy Jo; Alaee, Yasmin; Ranganathan, Radha

2014-01-01

Distributions of lysopalmitoylphosphatidylcholine (LPPC), palmitic acid (PA) and their 1:1 mixtures between water and dipalmitoylphosphatidylcholine (DPPC) bilayer were determined using a fluorescence probe that selectively detects only the solutes in water. Water solute concentrations were obtained at each of several lipid concentrations. Dynamic Light Scattering experiments confirmed that the lipid/solute aggregates were vesicles in the concentration range investigated. Lipid concentration dependence of the solute component in water was fit to a thermodynamic model of solute distribution between two coexisting solvents. Water/bilayer partition coefficient and the free energy of transfer, for each of these solutes were determined from the fit. Main findings are: (1) Water/bilayer partition coefficient of solute is greater for 2 to 10% solute mole fraction than for 0 to 2%, signaling solute induced bilayer perturbation that increases bilayer solubility, beginning at 2% solute mole fraction. (2) Partition coefficients are in the order LPPC

Partitioning of Lysolipids, Fatty Acids and Their Mixtures in Aqueous Lipid Bilayers: Solute Concentration / Composition Effects

PubMed Central

Singh, Jasmeet; Lai, Amy Jo; Alaee, Yasmin; Ranganathan, Radha

2013-01-01

Distribution of lysopalmitoylphosphatidylcholine (LPPC), Palmitic acid (PA) and their 1:1 mixtures between water and dipalmitoylphosphatidylcholine (DPPC) bilayer were determined using a fluorescence probe that selectively detects only the solutes in water. Water solute concentrations were obtained at each of several lipid concentrations. Dynamic Light Scattering experiments confirmed that the lipid/solute aggregates were vesicles in the concentration range investigated. Lipid concentration dependence of the solute component in water was fit to a thermodynamic model of solute distribution between two coexisting solvents. Water/bilayer partition coefficient and the free energy of transfer, for each of these solutes were determined from the fit. Main findings are: (1) Water/bilayer partition coefficient of solute is greater for 2 to 10 % solute mole fraction than for 0 to 2 %, signaling solute induced bilayer perturbation that increases bilayer solubility, beginning at 2 % solute mole fraction. (2) Partition coefficients are in the order LPPC

NIR studies of cholesterol-dependent structural modification of the model lipid bilayer doped with inhalation anesthetics

NASA Astrophysics Data System (ADS)

Kuć, Marta; Cieślik-Boczula, Katarzyna; Rospenk, Maria

2018-06-01

The influence of cholesterol on the structure of the model lipid bilayers treated with inhalation anesthetics (enflurane, isoflurane, sevoflurane and halothane) was investigated employing near-infrared (NIR) spectroscopy combined with the Principal Component Analysis (PCA). The conformational changes occurring in the hydrophobic area of the lipid bilayers were analyzed using the first overtones of symmetric (2νs) and antisymmetric (2νas) stretching vibrations of the CH2 groups of lipid aliphatic chains. The temperature values of chain-melting phase transition (Tm) of anesthetic-mixed dipalmitoylphosphatidylcholine (DPPC)/cholesterol and dipalmitoylphosphatidylglycerol (DPPG)/cholesterol membranes, which were obtained from the PCA analysis, were compared with cholesterol-free DPPC and DPPG bilayers mixed with inhalation anesthetics.

Bilayered graphene/h-BN with folded holes as new nanoelectronic materials: modeling of structures and electronic properties

PubMed Central

Chernozatonskii, Leonid A.; Demin, Viсtor A.; Bellucci, Stefano

2016-01-01

The latest achievements in 2-dimensional (2D) material research have shown the perspective use of sandwich structures in nanodevices. We demonstrate the following generation of bilayer materials for electronics and optoelectronics. The atomic structures, the stability and electronic properties of Moiré graphene (G)/h-BN bilayers with folded nanoholes have been investigated theoretically by ab-initio DFT method. These perforated bilayers with folded hole edges may present electronic properties different from the properties of both graphene and monolayer nanomesh structures. The closing of the edges is realized by C-B(N) bonds that form after folding the borders of the holes. Stable ≪round≫ and ≪triangle≫ holes organization are studied and compared with similar hole forms in single layer graphene. The electronic band structures of the considered G/BN nanomeshes reveal semiconducting or metallic characteristics depending on the sizes and edge terminations of the created holes. This investigation of the new types of G/BN nanostructures with folded edges might provide a directional guide for the future of this emerging area. PMID:27897237

Density functional studies of the defect-induced electronic structure modifications in bilayer boronitrene

NASA Astrophysics Data System (ADS)

Ukpong, A. M.; Chetty, N.

2012-05-01

The van der Waals interaction-corrected density functional theory is used in this study to investigate the formation, energetic stability, and inter-layer cohesion in bilayer hexagonal boronitrene. The effect of inter-layer separation on the electronic structure is systematically investigated. The formation and energetic stability of intrinsic defects are also investigated at the equilibrium inter-layer separation. It is found that nonstoichiometric defects, and their complexes, that induce excess nitrogen or excess boron, in each case, are relatively more stable in the atmosphere that corresponds to the excess atomic species. The modifications of the electronic structure due to formation of complexes are also investigated. It is shown that van der Waals density functional theory gives an improved description of the cohesive properties but not the electronic structure in bilayer boronitrene compared to other functionals. We identify energetically favourable topological defects that retain the energy gap in the electronic structure, and discuss their implications for band gap engineering in low-n layer boronitrene insulators. The relative strengths and weaknesses of the functionals in predicting the properties of bilayer boronitrene are also discussed.

Impact of amphiphilic molecules on the structure and stability of homogeneous sphingomyelin bilayer: Insights from atomistic simulations

NASA Astrophysics Data System (ADS)

Kumari, Pratibha; Kaur, Supreet; Sharma, Shobha; Kashyap, Hemant K.

2018-04-01

Modulation of lipid membrane properties due to the permeation of amphiphiles is an important biological process pertaining to many applications in the field of pharmaceutics, toxicology, and biotechnology. Sphingolipids are both structural and functional lipids that constitute an important component of mechanically stable and chemically resistant outer leaflets of plasma membranes. Here, we present an atomistic molecular dynamics simulation study to appreciate the concentration-dependent effects of small amphiphilic molecules, such as ethanol, acetone, and dimethyl sulfoxide (DMSO), on the structure and stability of a fully hydrated homogeneous N-palmitoyl-sphingomyelin (PSM) bilayer. The study reveals an increase in the lateral expansion of the bilayer along with disordering of the hydrophobic lipid tails on increasing the concentration of ethanol. At higher concentrations of ethanol, rupturing of the bilayer is quite evident through the analysis of partial electron density profiles and lipid tail order parameters. For ethanol containing systems, permeation of water molecules in the hydrophobic part of the bilayer is allowed through local defects made due to the entry of ethanol molecules via ethanol-ethanol and ethanol-PSM hydrogen bonds. Moreover, the extent of PSM-PSM hydrogen bonding decreases with increasing ethanol concentration. On the other hand, acetone and DMSO exhibit minimal effects on the stability of the PSM bilayer at their lower concentrations, but at higher concentrations they tend to enhance the stability of the bilayer. The simulated potential of mean force (PMF) profiles for the translocation of the three solutes studied reveal that the free-energy of transfer of an ethanol molecule across the PSM lipid head region is lower than that for acetone and DMSO molecules. However, highest free-energy rise in the core hydrophobic part of the bilayer is observed for the DMSO molecule, whereas the ethanol and acetone PMF profiles show a lower barrier in the hydrophobic region of the bilayer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Jianhui; Nickels, Jonathan; Katsaras, John

Spatial organization within lipid bilayers is an important feature for a range of biological processes. Leaflet compositional asymmetry and lateral lipid organization are just two of the ways in which membrane structure appears to be more complex than initially postulated by the fluid mosaic model. This raises the question of how the phase behavior in one bilayer leaflet may affect the apposing leaflet and how one begins to construct asymmetric model systems to investigate these interleaflet interactions. In this paper, we report on all-atom molecular dynamics simulations (a total of 4.1 μs) of symmetric and asymmetric bilayer systems composed ofmore » liquid-ordered (Lo) or liquid-disordered (Ld) leaflets, based on the nanodomain-forming POPC/DSPC/cholesterol system. We begin by analyzing an asymmetric bilayer with leaflets derived from simulations of symmetric Lo and Ld bilayers. In this system, we observe that the properties of the Lo and Ld leaflets are similar to those of the Lo and Ld leaflets in corresponding symmetric systems. However, it is not obvious that mixing the equilibrium structures of their symmetric counterparts is the most appropriate way to construct asymmetric bilayers nor that these structures will manifest interleaflet couplings that lead to domain registry/antiregistry. We therefore constructed and simulated four additional asymmetric bilayer systems by systematically adding or removing lipids in the Ld leaflet to mimic potential density fluctuations. We find that the number of lipids in the Ld leaflet affects its own properties, as well as those of the apposing Lo leaflet. Collectively, the simulations reveal the presence of weak acyl chain interdigitation across bilayer leaflets, suggesting that interdigitation alone does not contribute significantly to the interleaflet coupling in nonphase-separated bilayers of this chemical composition. Finally, however, the properties of both leaflets appear to be sensitive to changes in in-plane lipid packing, possibly providing a mechanism for interleaflet coupling by modulating local density and/or curvature fluctuations.« less

High-Aspect-Ratio Ridge Structures Induced by Plastic Deformation as a Novel Microfabrication Technique.

PubMed

Takei, Atsushi; Jin, Lihua; Fujita, Hiroyuki; Takei, A; Fujita, H; Jin, Lihua

2016-09-14

Wrinkles on thin film/elastomer bilayer systems provide functional surfaces. The aspect ratio of these wrinkles is critical to their functionality. Much effort has been dedicated to creating high-aspect-ratio structures on the surface of bilayer systems. A highly prestretched elastomer attached to a thin film has recently been shown to form a high-aspect-ratio structure, called a ridge structure, due to a large strain induced in the elastomer. However, the prestretch requirements of the elastomer during thin film attachment are not compatible with conventional thin film deposition methods, such as spin coating, dip coating, and chemical vapor deposition (CVD). Thus, the fabrication method is complex, and ridge structure formation is limited to planar surfaces. This paper presents a new and simple method for constructing ridge structures on a nonplanar surface using a plastic thin film/elastomer bilayer system. A plastic thin film is attached to a stress-free elastomer, and the resulting bilayer system is highly stretched one- or two-dimensionally. Upon the release of the stretch load, the deformation of the elastomer is reversible, while the plastically deformed thin film stays elongated. The combination of the length mismatch and the large strain induced in the elastomer generates ridge structures. The morphology of the plastic thin film/elastomer bilayer system is experimentally studied by varying the physical parameters, and the functionality and the applicability to a nonplanar surface are demonstrated. Finally, we simulate the effect of plasticity on morphology. This study presents a new technique for generating microscale high-aspect-ratio structures and its potential for functional surfaces.

Effects of Dimethyl Sulfoxide on Surface Water near Phospholipid Bilayers.

PubMed

Lee, Yuno; Pincus, Philip A; Hyeon, Changbong

2016-12-06

Despite much effort to probe the properties of dimethyl sulfoxide (DMSO) solution, the effects of DMSO on water, especially near plasma membrane surfaces, still remain elusive. By performing molecular dynamics simulations at varying DMSO concentrations (X DMSO ), we study how DMSO affects structural and dynamical properties of water in the vicinity of phospholipid bilayers. As proposed by a number of experiments, our simulations confirm that DMSO induces dehydration from bilayer surfaces and disrupts the H-bond structure of water. However, DMSO-enhanced water diffusivity at solvent-bilayer interfaces, an intriguing discovery reported by a spin-label measurement, is not confirmed in our simulations. To resolve this discrepancy, we examine the location of the spin label (Tempo) relative to the solvent-bilayer interface. In accord with the evidence in the literature, our simulations, which explicitly model Tempo-phosphatidylcholine, find that the Tempo moiety is equilibrated at ∼8-10 Å below the bilayer surface. Furthermore, the DMSO-enhanced surface-water diffusion is confirmed only when water diffusion is analyzed around the Tempo moiety that is immersed below the bilayer surface, which implies that the experimentally detected signal of water using Tempo stems from the interior of bilayers, not from the interface. Our analysis finds that the increase of water diffusion below the bilayer surface is coupled to the increase of area per lipid with an increasing X DMSO (≲10mol%). Underscoring the hydrophobic nature of the Tempo moiety, our study calls for careful re-evaluation of the use of Tempo in measurements on lipid bilayer surfaces. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

The cubicon method for concentrating membrane proteins in the cubic mesophase.

PubMed

Ma, Pikyee; Weichert, Dietmar; Aleksandrov, Luba A; Jensen, Timothy J; Riordan, John R; Liu, Xiangyu; Kobilka, Brian K; Caffrey, Martin

2017-09-01

The lipid cubic phase (in meso) method is an important approach for generating crystals and high-resolution X-ray structures of integral membrane proteins. However, as a consequence of instability, it can be impossible-using traditional methods-to concentrate certain membrane proteins and complexes to values suitable for in meso crystallization and structure determination. The cubicon method described here exploits the amphiphilic nature of membrane proteins and their natural tendency to partition preferentially into lipid bilayers from aqueous solution. Using several rounds of reconstitution, the protein concentration in the bilayer of the cubic mesophase can be ramped up stepwise from less than a milligram per milliliter to tens of milligrams per milliliter for crystallogenesis. The general applicability of the method is demonstrated with five integral membrane proteins: the β 2 -adrenergic G protein-coupled receptor (β 2 AR), the peptide transporter (PepT St ), diacylglycerol kinase (DgkA), the alginate transporter (AlgE) and the cystic fibrosis transmembrane conductance regulator (CFTR). In the cases of β 2 AR, PepT St , DgkA and AlgE, an effective 20- to 45-fold concentration was realized, resulting in a protein-laden mesophase that allowed the formation of crystals using the in meso method and structure determination to resolutions ranging from 2.4 Å to 3.2 Å. In addition to opening up in meso crystallization to a broader range of integral membrane protein targets, the cubicon method should find application in situations that require membrane protein reconstitution in a lipid bilayer at high concentrations. These applications include functional and biophysical characterization studies for ligand screening, drug delivery, antibody production and protein complex formation. A typical cubicon experiment can be completed in 3-5 h.

Synergistic interactions of lipids and myelin basic protein

NASA Astrophysics Data System (ADS)

Hu, Yufang; Doudevski, Ivo; Wood, Denise; Moscarello, Mario; Husted, Cynthia; Genain, Claude; Zasadzinski, Joseph A.; Israelachvili, Jacob

2004-09-01

This report describes force measurements and atomic force microscope imaging of lipid-protein interactions that determine the structure of a model membrane system that closely mimics the myelin sheath. Our results suggest that noncovalent, mainly electrostatic and hydrophobic, interactions are responsible for the multilamellar structure and stability of myelin. We find that myelin basic protein acts as a lipid coupler between two apposed bilayers and as a lipid "hole-filler," effectively preventing defect holes from developing. From our protein-mediated-adhesion and force-distance measurements, we develop a simple quantitative model that gives a reasonably accurate picture of the molecular mechanism and adhesion of bilayer-bridging proteins by means of noncovalent interactions. The results and model indicate that optimum myelin adhesion and stability depend on the difference between, rather than the product of, the opposite charges on the lipid bilayers and myelin basic protein, as well as on the repulsive forces associated with membrane fluidity, and that small changes in any of these parameters away from the synergistically optimum values can lead to large changes in the adhesion or even its total elimination. Our results also show that the often-asked question of which membrane species, the lipids or the proteins, are the "important ones" may be misplaced. Both components work synergistically to provide the adhesion and overall structure. A better appreciation of the mechanism of this synergy may allow for a better understanding of stacked and especially myelin membrane structures and may lead to better treatments for demyelinating diseases such as multiple sclerosis. lipid-protein interactions | myelin membrane structure | membrane adhesion | membrane regeneration/healing | demyelinating diseases

Biaxial mechanics and inter-lamellar shearing of stem-cell seeded electrospun angle-ply laminates for annulus fibrosus tissue engineering.

PubMed

Driscoll, Tristan P; Nakasone, Ryan H; Szczesny, Spencer E; Elliott, Dawn M; Mauck, Robert L

2013-06-01

The annulus fibrosus (AF) of the intervertebral disk plays a critical role in vertebral load transmission that is heavily dependent on the microscale structure and composition of the tissue. With degeneration, both structure and composition are compromised, resulting in a loss of AF mechanical function. Numerous tissue engineering strategies have addressed the issue of AF degeneration, but few have focused on recapitulation of AF microstructure and function. One approach that allows for generation of engineered AF with appropriate (+/-)30° lamellar microstructure is the use of aligned electrospun scaffolds seeded with mesenchymal stem cells (MSCs) and assembled into angle-ply laminates (APL). Previous work indicates that opposing lamellar orientation is necessary for development of near native uniaxial tensile properties. However, most native AF tensile loads are applied biaxially, as the disk is subjected to multi-axial loads and is constrained by its attachments to the vertebral bodies. Thus, the objective of this study was to evaluate the biaxial mechanical response of engineered AF bilayers, and to determine the importance of opposing lamellar structure under this loading regime. Opposing bilayers, which replicate native AF structure, showed a significantly higher modulus in both testing directions compared to parallel bilayers, and reached ∼60% of native AF biaxial properties. Associated with this increase in biaxial properties, significantly less shear, and significantly higher stretch in the fiber direction, was observed. These results provide additional insight into native tissue structure-function relationships, as well as new benchmarks for engineering functional AF tissue constructs. Copyright © 2013 Orthopaedic Research Society.

Transmembrane proteins in the Protein Data Bank: identification and classification.

PubMed

Tusnády, Gábor E; Dosztányi, Zsuzsanna; Simon, István

2004-11-22

Integral membrane proteins play important roles in living cells. Although these proteins are estimated to constitute 25% of proteins at a genomic scale, the Protein Data Bank (PDB) contains only a few hundred membrane proteins due to the difficulties with experimental techniques. The presence of transmembrane proteins in the structure data bank, however, is quite invisible, as the annotation of these entries is rather poor. Even if a protein is identified as a transmembrane one, the possible location of the lipid bilayer is not indicated in the PDB because these proteins are crystallized without their natural lipid bilayer, and currently no method is publicly available to detect the possible membrane plane using the atomic coordinates of membrane proteins. Here, we present a new geometrical approach to distinguish between transmembrane and globular proteins using structural information only and to locate the most likely position of the lipid bilayer. An automated algorithm (TMDET) is given to determine the membrane planes relative to the position of atomic coordinates, together with a discrimination function which is able to separate transmembrane and globular proteins even in cases of low resolution or incomplete structures such as fragments or parts of large multi chain complexes. This method can be used for the proper annotation of protein structures containing transmembrane segments and paves the way to an up-to-date database containing the structure of all known transmembrane proteins and fragments (PDB_TM) which can be automatically updated. The algorithm is equally important for the purpose of constructing databases purely of globular proteins.

Fabrication and Optimization of Bilayered Nanoporous Anodic Alumina Structures as Multi-Point Interferometric Sensing Platform

PubMed Central

Nemati, Mahdieh; Santos, Abel

2018-01-01

Herein, we present an innovative strategy for optimizing hierarchical structures of nanoporous anodic alumina (NAA) to advance their optical sensing performance toward multi-analyte biosensing. This approach is based on the fabrication of multilayered NAA and the formation of differential effective medium of their structure by controlling three fabrication parameters (i.e., anodization steps, anodization time, and pore widening time). The rationale of the proposed concept is that interferometric bilayered NAA (BL-NAA), which features two layers of different pore diameters, can provide distinct reflectometric interference spectroscopy (RIfS) signatures for each layer within the NAA structure and can therefore potentially be used for multi-point biosensing. This paper presents the structural fabrication of layered NAA structures, and the optimization and evaluation of their RIfS optical sensing performance through changes in the effective optical thickness (EOT) using quercetin as a model molecule. The bilayered or funnel-like NAA structures were designed with the aim of characterizing the sensitivity of both layers of quercetin molecules using RIfS and exploring the potential of these photonic structures, featuring different pore diameters, for simultaneous size-exclusion and multi-analyte optical biosensing. The sensing performance of the prepared NAA platforms was examined by real-time screening of binding reactions between human serum albumin (HSA)-modified NAA (i.e., sensing element) and quercetin (i.e., analyte). BL-NAAs display a complex optical interference spectrum, which can be resolved by fast Fourier transform (FFT) to monitor the EOT changes, where three distinctive peaks were revealed corresponding to the top, bottom, and total layer within the BL-NAA structures. The spectral shifts of these three characteristic peaks were used as sensing signals to monitor the binding events in each NAA pore in real-time upon exposure to different concentrations of quercetin. The multi-point sensing performance of BL-NAAs was determined for each pore layer, with an average sensitivity and low limit of detection of 600 nm (mg mL−1)−1 and 0.14 mg mL−1, respectively. BL-NAAs photonic structures have the capability to be used as platforms for multi-point RIfS sensing of biomolecules that can be further extended for simultaneous size-exclusion separation and multi-analyte sensing using these bilayered nanostructures. PMID:29415436

Hematite/silica nanoparticle bilayers on mica: AFM and electrokinetic characterization.

PubMed

Morga, Maria; Adamczyk, Zbigniew; Kosior, Dominik; Oćwieja, Magdalena

2018-06-06

Quantitative studies on self-assembled hematite/silica nanoparticle (NP) bilayers on mica were performed by applying scanning electron microscopy (SEM), atomic force microscopy (AFM), and streaming potential measurements. The coverage of the supporting hematite layers was adjusted by changing the bulk concentration of the suspension and the deposition time. The coverage was determined by direct enumeration of deposited particles from AFM images and SEM micrographs. Afterward, silica nanoparticle monolayers were assembled under diffusion-controlled transport. A unique functional relationship was derived connecting the silica coverage with the hematite precursor layer coverage. The formation of the hematite monolayer and the hematite/silica bilayer was also monitored in situ by streaming potential measurements. It was confirmed that the zeta potential of the bilayers was independent of the supporting layer coverage, exceeding 0.15. These measurements were theoretically interpreted in terms of the general electrokinetic model that allowed for deriving a formula for calculating nanoparticle coverage in the bilayers. Additionally, from desorption experiments, the interactions among hematite/silica particles in the bilayers were determined using DLVO theory. These results facilitate the development of a robust method of preparing nanoparticle bilayers with controlled properties, with potential applications in catalytic processes.

Interaction of cholesterol-conjugated ionizable amino lipids with biomembranes: lipid polymorphism, structure-activity relationship, and implications for siRNA delivery.

PubMed

Zhang, Jingtao; Fan, Haihong; Levorse, Dorothy A; Crocker, Louis S

2011-08-02

Delivery of siRNA is a major obstacle to the advancement of RNAi as a novel therapeutic modality. Lipid nanoparticles (LNP) consisting of ionizable amino lipids are being developed as an important delivery platform for siRNAs, and significant efforts are being made to understand the structure-activity relationship (SAR) of the lipids. This article uses a combination of small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) to evaluate the interaction between cholesterol-conjugated ionizable amino lipids and biomembranes, focusing on an important area of lipid SAR--the ability of lipids to destabilize membrane bilayer structures and facilitate endosomal escape. In this study, cholesterol-conjugated amino lipids were found to be effective in increasing the order of biomembranes and also highly effective in inducing phase changes in biological membranes in vitro (i.e., the lamellar to inverted hexagonal phase transition). The phase transition temperatures, determined using SAXS and DSC, serve as an indicator for ranking the potency of lipids to destabilize endosomal membranes. It was found that the bilayer disruption ability of amino lipids depends strongly on the amino lipid concentration in membranes. Amino lipids with systematic variations in headgroups, the extent of ionization, tail length, the degree of unsaturation, and tail asymmetry were evaluated for their bilayer disruption ability to establish SAR. Overall, it was found that the impact of these lipid structure changes on their bilayer disruption ability agrees well with the results from a conceptual molecular "shape" analysis. Implications of the findings from this study for siRNA delivery are discussed. The methods reported here can be used to support the SAR screening of cationic lipids for siRNA delivery, and the information revealed through the study of the interaction between cationic lipids and biomembranes will contribute significantly to the design of more efficient siRNA delivery vehicles.

SFG studies on interactions between antimicrobial peptides and supported lipid bilayers.

PubMed

Chen, Xiaoyun; Chen, Zhan

2006-09-01

The mode of action of antimicrobial peptides (AMPs) in disrupting cell membrane bilayers is of fundamental importance in understanding the efficiency of different AMPs, which is crucial to design antibiotics with improved properties. Recent developments in the field of sum frequency generation (SFG) vibrational spectroscopy have made it a powerful and unique biophysical technique in investigating the interactions between AMPs and a single substrate supported planar lipid bilayer. We will review some of the recent progress in applying SFG to study membrane lipid bilayers and discuss how SFG can provide novel information such as real-time bilayer structure change and AMP orientation during AMP-lipid bilayer interactions in a very biologically relevant manner. Several examples of applying SFG to monitor such interactions between AMPs and a dipalmitoyl phosphatidylglycerol (DPPG) bilayer are presented. Different modes of actions are observed for melittin, tachyplesin I, d-magainin 2, MSI-843, and a synthetic antibacterial oligomer, demonstrating that SFG is very effective in the study of AMPs and AMP-lipid bilayer interactions.

Changes in Phosphatidylcholine Headgroup Tilt and Water Order Induced by Monovalent Salts: Molecular Dynamics Simulations

PubMed Central

Sachs, Jonathan N.; Nanda, Hirsh; Petrache, Horia I.; Woolf, Thomas B.

2004-01-01

The association between monovalent salts and neutral lipid bilayers is known to influence global bilayer structural properties such as headgroup conformational fluctuations and the dipole potential. The local influence of the ions, however, has been unknown due to limited structural resolution of experimental methods. Molecular dynamics simulations are used here to elucidate local structural rearrangements upon association of a series of monovalent Na+ salts to a palmitoyl-oleoyl-phosphatidylcholine bilayer. We observe association of all ion types in the interfacial region. Larger anions, which are meant to rationalize data regarding a Hofmeister series of anions, bind more deeply within the bilayer than either Cl− or Na+. Although the simulations are able to reproduce experimentally measured quantities, the analysis is focused on local properties currently invisible to experiments, which may be critical to biological systems. As such, for all ion types, including Cl−, we show local ion-induced perturbations to headgroup tilt, the extent and direction of which is sensitive to ion charge and size. Additionally, we report salt-induced ordering of the water well beyond the interfacial region, which may be significant in terms of hydration repulsion between stacked bilayers. PMID:15189873

A New Route to Liposil Formation by an Interfacial Sol-Gel Process Confined by Lipid Bilayer.

PubMed

Shen, Shukun; Yang, Lu; Lu, Yaxing; Chen, Jian-Gang; Song, Shaofei; Hu, Daodao; Parikh, Atul

2015-11-18

We report a new and simple approach to prepare a class of silica-reinforced liposomes with hybrid core-shell nanostructures. The amphiphilic natural structure of lipids was exploited to sequester hydrophobic molecules, namely precursor TEOS and pyrene, in the hydrophobic midplane of liposomal bilayer assemblies in the aqueous phase. Subsequent interfacial hydrolysis of TEOS at the bilayer/water interface and ensuing condensation within the hydrophobic interstices of the lipid bilayer drives silica formation in situ, producing a novel class of silica-lipid hybrid liposils. Structural characterization by scanning- and transmission electron microscopy confirm that the liposils so generated preserve closed topologies and size-monodipersity of the parent lecithin liposomes, and DSC-TGA and XRD measurements provide evidence for the silica coating. Monitoring fluorescence measurements using embedded pyrene yield detailed information on microenvironment changes, which occur during sol-gel process and shed light on the structural evolution during silica formation. We envisage that liposils formed by this simple, new approach, exploiting the hydrophobic core of the lipid bilayer to spatially localize silica-forming precursors enables preparation of stable liposils exhibiting capacity for cargo encapsulation, bicompatibility, and fluorescence monitoring, more generally opening a window for construction of stable, functional hybrid materials.

Topological magnetic phase in LaMnO3 (111) bilayer

NASA Astrophysics Data System (ADS)

Weng, Yakui; Huang, Xin; Yao, Yugui; Dong, Shuai

Candidates for correlated topological insulators, originated from the spin-orbit coupling as well as Hubbard type correlation, are expected in the (111) bilayer of perovskite-structural transition-metal oxides. Based on the first-principles calculation and tight-binding model, the electronic structure of a LaMnO3 (111) bilayer sandwiched in LaScO3 barriers has been investigated. For the ideal undistorted perovskite structure, the Fermi energy of LaMnO3 (111) bilayer just stays at the Dirac point, rendering a semi-metal (graphene-like) which is also a half-metal (different from graphene nor previous studied LaNiO3 (111) bilayer). The Dirac cone can be opened by the spin-orbit coupling, giving rise to nontrivial topological bands corresponding to the (quantized) anomalous Hall effect. For the realistic orthorhombic distorted lattice, the Dirac point moves with increasing Hubbard repulsion (or equivalent Jahn-Teller distortion). Finally, a Mott gap opens, establishing a phase boundary between the Mott insulator and topological magnetic insulator. Our calculation finds that the gap opened by spin-orbit coupling is much smaller in the orthorhombic distorted lattice (~ 1 . 7 meV) than the undistorted one (~11 meV).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rai, Durgesh K.; Sharma, Veerendra K.; Anunciado, Divina

The interaction between lipid bilayers and Amyloid β peptide (Aβ) plays a critical role in proliferation of Alzheimer’s disease (AD). AD is expected to affect one in every 85 humans by 2050, and therefore, deciphering the interplay of Aβ and lipid bilayers at the molecular level is of profound importance. In this work, we applied an array of neutron scattering methods to study the structure and dynamics of Aβ(1–40) interacting 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) bilayers. In the structural investigations of lipid bilayer’s response to Aβ binding, Small Angle Neutron Scattering and Neutron Membrane Diffraction revealed that the Aβ anchors firmly to themore » highly charged DMPG bilayers in the interfacial region between water and hydrocarbon chain, and it doesn’t penetrate deeply into the bilayer. This association mode is substantiated by the dynamics studies with high resolution Quasi-Elastic Neutron Scattering experiments, showing that the addition of Aβ mainly affects the slower lateral motion of lipid molecules, especially in the fluid phase, but not the faster internal motion. The results revealed that Aβ associates with the highly charged membrane in surface with limited impact on the structure, but the altered membrane dynamics could have more influence on other membrane processes.« less

Asymmetric or symmetric bilayer formation during oblique drop impact depends on rheological properties of saturated and unsaturated lipid monolayers.

PubMed

Vranceanu, Marcel; Terinte, Nicoleta; Nirschl, Hermann; Leneweit, Gero

2011-02-01

Bilayer structures are formed by approaching two liquid surfaces with phospholipid monolayers, which are brought into contact by oblique drop impact on a liquid surface. Asymmetric bilayers can be produced by the coupling of drop and target monolayers. In contrast, symmetric bilayers or multilayers are formed by collapse of the compressed target monolayer. We show that under all studied conditions bilayer/multilayer synthesis takes place. The experimental conditions for the synthesis of asymmetric or symmetric bilayers are described quantitatively in terms of the surface rheological (surface elasticity and dilational viscosity) and the hydrodynamical parameters (Weber number and impact angle). The composition and mechanical properties of the phospholipid monolayers strongly influences the patterns of drop impact and the bilayer/multilayer formation. Cholesterol stiffens unsaturated phospholipid monolayers and fluidifies saturated monolayers. All monolayers form asymmetric vesicle-like structures, which are stable in the aqueous medium. Additionally, unsaturated phospholipid monolayers without cholesterol form symmetric vesicles by folding parts of the target monolayer. Sufficient presence of cholesterol in unsaturated phospholipid monolayers inhibits the folding of the target monolayer and the subsequent formation of symmetric bilayers. The rheological properties of saturated and unsaturated phospholipid monolayers and their mixtures with cholesterol are discussed. Based on drop impact results it is shown that the state of a so far undefined region in the DPPC/cholesterol phase diagram is a fluid phase. Copyright © 2010 Elsevier Inc. All rights reserved.

Thermally induced fracture for core-veneered dental ceramic structures.

PubMed

Zhang, Zhongpu; Guazzato, Massimiliano; Sornsuwan, Tanapon; Scherrer, Susanne S; Rungsiyakull, Chaiy; Li, Wei; Swain, Michael V; Li, Qing

2013-09-01

Effective and reliable clinical uses of dental ceramics necessitate an insightful analysis of the fracture behaviour under critical conditions. To better understand failure characteristics of porcelain veneered to zirconia core ceramic structures, thermally induced cracking during the cooling phase of fabrication is studied here by using the extended finite element method (XFEM). In this study, a transient thermal analysis of cooling is conducted first to determine the temperature distributions. The time-dependent temperature field is then imported to the XFEM model for viscoelastic thermomechanical analysis, which predicts thermally induced damage and cracking at different time steps. Temperature-dependent material properties are used in both transient thermal and thermomechanical analyses. Three typical ceramic structures are considered in this paper, namely bi-layered spheres, squat cylinders and dental crowns with thickness ratios of either 1:2 or 1:1. The XFEM fracture patterns exhibit good agreement with clinical observation and the in vitro experimental results obtained from scanning electron microscopy characterization. The study reveals that fast cooling can lead to thermal fracture of these different bi-layered ceramic structures, and cooling rate (in terms of heat transfer coefficient) plays a critical role in crack initiation and propagation. By exploring different cooling rates, the heat transfer coefficient thresholds of fracture are determined for different structures, which are of clear clinical implication. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Interaction driven quantum Hall effect in artificially stacked graphene bilayers

PubMed Central

Iqbal, Muhammad Zahir; Iqbal, Muhammad Waqas; Siddique, Salma; Khan, Muhammad Farooq; Ramay, Shahid Mahmood; Nam, Jungtae; Kim, Keun Soo; Eom, Jonghwa

2016-01-01

The honeycomb lattice structure of graphene gives rise to its exceptional electronic properties of linear dispersion relation and its chiral nature of charge carriers. The exceptional electronic properties of graphene stem from linear dispersion relation and chiral nature of charge carries, originating from its honeycomb lattice structure. Here, we address the quantum Hall effect in artificially stacked graphene bilayers and single layer graphene grown by chemical vapor deposition. The quantum Hall plateaus started to appear more than 3 T and became clearer at higher magnetic fields up to 9 T. Shubnikov-de Hass oscillations were manifestly observed in graphene bilayers texture. These unusual plateaus may have been due to the layers interaction in artificially stacked graphene bilayers. Our study initiates the understanding of interactions between artificially stacked graphene layers. PMID:27098387

Interaction driven quantum Hall effect in artificially stacked graphene bilayers.

PubMed

Iqbal, Muhammad Zahir; Iqbal, Muhammad Waqas; Siddique, Salma; Khan, Muhammad Farooq; Ramay, Shahid Mahmood; Nam, Jungtae; Kim, Keun Soo; Eom, Jonghwa

2016-04-21

The honeycomb lattice structure of graphene gives rise to its exceptional electronic properties of linear dispersion relation and its chiral nature of charge carriers. The exceptional electronic properties of graphene stem from linear dispersion relation and chiral nature of charge carries, originating from its honeycomb lattice structure. Here, we address the quantum Hall effect in artificially stacked graphene bilayers and single layer graphene grown by chemical vapor deposition. The quantum Hall plateaus started to appear more than 3 T and became clearer at higher magnetic fields up to 9 T. Shubnikov-de Hass oscillations were manifestly observed in graphene bilayers texture. These unusual plateaus may have been due to the layers interaction in artificially stacked graphene bilayers. Our study initiates the understanding of interactions between artificially stacked graphene layers.

Thermally Strained Band Gap Engineering of Transition-Metal Dichalcogenide Bilayers with Enhanced Light-Matter Interaction toward Excellent Photodetectors.

PubMed

Wang, Sheng-Wen; Medina, Henry; Hong, Kuo-Bin; Wu, Chun-Chia; Qu, Yindong; Manikandan, Arumugam; Su, Teng-Yu; Lee, Po-Tsung; Huang, Zhi-Quan; Wang, Zhiming; Chuang, Feng-Chuan; Kuo, Hao-Chung; Chueh, Yu-Lun

2017-09-26

Integration of strain engineering of two-dimensional (2D) materials in order to enhance device performance is still a challenge. Here, we successfully demonstrated the thermally strained band gap engineering of transition-metal dichalcogenide bilayers by different thermal expansion coefficients between 2D materials and patterned sapphire structures, where MoS 2 bilayers were chosen as the demonstrated materials. In particular, a blue shift in the band gap of the MoS 2 bilayers can be tunable, displaying an extraordinary capability to drive electrons toward the electrode under the smaller driven bias, and the results were confirmed by simulation. A model to explain the thermal strain in the MoS 2 bilayers during the synthesis was proposed, which enables us to precisely predict the band gap-shifted behaviors on patterned sapphire structures with different angles. Furthermore, photodetectors with enhancement of 286% and 897% based on the strained MoS 2 on cone- and pyramid-patterned sapphire substrates were demonstrated, respectively.

Structural and electro-optical properties of bilayer graphyne like BN sheet

NASA Astrophysics Data System (ADS)

Behzad, Somayeh

2016-12-01

The structural, electronic and optical properties of bilayer graphyne like BN sheet (BNyne) with different stacking manners have been explored by the first-principles calculations. The stabilities of α-BNyne bilayers with different stacking manners are compared. The α-BNyne Bilayers have wide band gaps. Compared to the single α-BNyne, the numbers of energy bands are doubled due to the interlayer interactions and the band gap is reduced. The AB-I configuration has a direct band gap while the band gap becomes indirect for AA-II. The calculated ε2 (ω) of bilayer α-BNyne for (Eǁx) is similar to that of the monolayer α-BNyne, except for the small changes of peak positions and increasing of peak intensities. For (Eǁz), the first absorption peak occures at 3.86 eV, and the prominant peak of monolayer at 9.17 eV becomes broadened. These changes are related to the new transitions resulting from the band splitting.

Enhancement of resistive switching properties in Al2O3 bilayer-based atomic switches: multilevel resistive switching.

PubMed

Vishwanath, Sujaya Kumar; Woo, Hyunsuk; Jeon, Sanghun

2018-06-08

Atomic switches are considered to be building blocks for future non-volatile data storage and internet of things. However, obtaining device structures capable of ultrahigh density data storage, high endurance, and long data retention, and more importantly, understanding the switching mechanisms are still a challenge for atomic switches. Here, we achieved improved resistive switching performance in a bilayer structure containing aluminum oxide, with an oxygen-deficient oxide as the top switching layer and stoichiometric oxide as the bottom switching layer, using atomic layer deposition. This bilayer device showed a high on/off ratio (10 5 ) with better endurance (∼2000 cycles) and longer data retention (10 4 s) than single-oxide layers. In addition, depending on the compliance current, the bilayer device could be operated in four different resistance states. Furthermore, the depth profiles of the hourglass-shaped conductive filament of the bilayer device was observed by conductive atomic force microscopy.

Direct growth of graphene-dielectric bi-layer structure on device substrates from Si-based polymer

NASA Astrophysics Data System (ADS)

Seo, Hong-Kyu; Kim, Kyunghun; Min, Sung-Yong; Lee, Yeongjun; Eon Park, Chan; Raj, Rishi; Lee, Tae-Woo

2017-06-01

To facilitate the utilization of graphene films in conventional semiconducting devices (e.g. transistors and memories) which includes an insulating layer such as gate dielectric, facile synthesis of bi-layers composed of a graphene film and an insulating layer by one-step thermal conversion will be very important. We demonstrate a simple, inexpensive, scalable and patternable process to synthesize graphene-dielectric bi-layer films from solution-processed polydimethylsiloxane (PDMS) under a Ni capping layer. This method fabricates graphene-dielectric bi-layer structure simultaneously directly on substrate by thermal conversion of PDMS without using additional graphene transfer and patterning process or formation of an expensive dielectric layer, which makes the device fabrication process much easier. The graphene-dielectric bi-layer on a conducting substrate was used in bottom-contact pentacene field-effect transistors that showed ohmic contact and small hysteresis. Our new method will provide a way to fabricate flexible electronic devices simply and inexpensively.

Interaction of a Model Peptide with a Water--Bilayer System

NASA Technical Reports Server (NTRS)

Pohorille, A.; Wilson, M. A.

1994-01-01

We discuss a molecular dynamics study of the alanine dipeptide at the interface between water and a glycerol-1-monooleate (GMO) bilayer. The dipeptide is interfacially active and incorporates into the bilayer without disrupting its structure. The interfacial region that is readily penetrated by the dipeptide spans the entire head group portion of the bilayer. The polar groups of the alanine dipeptide mostly remain well solvated by water and the oxygen atoms of GMO, and conformations of the dipeptide are characterized by (phi, psi) angles typical of alpha-helix and beta-sheet structures. When the molecule is deeper in the bilayer, the C(sub 7eq) state also becomes stable. The barrier to the isomerization reaction at the interface is lower than in bulk phases. After 7 ns of trajectories, the system is not fully equilibrated, due to slow collective motions involving GMO head groups. These result in decreased mobility and lower rates of isomerization of the dipeptide at the interface.

Contact and Bandgap Engineering in Two Dimensional Crystal

NASA Astrophysics Data System (ADS)

Chu, Tao

At the heart of semiconductor research, bandgap is one of the key parameters for materials and determine their applications in modern technologies. For traditional bulk semiconductors, the bandgap is determined by the chemical composition and specific arrangement of the crystal lattices, and usually invariant during the device operation. Nevertheless, it is highly desirable for many optoelectronic and electronic applications to have materials with continuously tunable bandgap available. In the past decade, 2D layered materials including graphene and transition metal dichalcogenides (TMDs) have sparked interest in the scientific community, owing to their unique material properties and tremendous potential in various applications. Among many newly discovered properties that are non-existent in bulk materials, the strong in-plane bonding and weak van der Waals inter-planar interaction in these 2D layered structures leads to a widely tunable bandgap by electric field. This provides an extra knob to engineer the fundamental material properties and open a new design space for novel device operation. This thesis focuses on this field controlled dynamic bandgap and can be divided into three parts: (1) bilayer graphene is the first known 2D crystal with a bandgap can be continuously tuned by electric field. However, the electrical transport bandgaps is much smaller than both theoretical predictions and extracted bandgaps from optical measurements. In the first part of the thesis, the limiting factors of preventing achieving a large transport bandgap in bilayer graphene are investigated and different strategies to achieve a large transport bandgap are discussed, including the vertically scaling of gate oxide and patterning channel into ribbon structure. With a record large transport bandgap of ~200meV, a dual-gated semiconducting bilayer graphene P/N junction with extremely scaled gap of 20nm in-between is fabricated. A tunable local maxima feature, associated with 1D vHs DOS at the band edge of bilayer graphene, was experimentally observed in transport for the first time. (2) The bandgap of bilayer MoS2 is also predicted to be continuously tuned to zero by applying a perpendicular electric field. Here, the first experimental realization of tuning the bandgap of bilayer MoS2 by a vertical electric field is presented. An analytical approach utilizing the threshold voltages from ambipolar characteristics is employed to quantitatively extract bandgaps, which is further benchmarked by temperature dependent bandgap measurements and photoluminescence measurements. (3) Few layer graphene is employed as an example to demonstrate a novel self-aligned edge contacting scheme for layered material systems.

Do sterols reduce proton and sodium leaks through lipid bilayers?

PubMed

Haines, T H

2001-07-01

Proton and/or sodium electrochemical gradients are critical to energy handling at the plasma membranes of all living cells. Sodium gradients are used for animal plasma membranes, all other living organisms use proton gradients. These chemical and electrical gradients are either created by a cation pumping ATPase or are created by photons or redox, used to make ATP. It has been established that both hydrogen and sodium ions leak through lipid bilayers at approximately the same rate at the concentration they occur in living organisms. Although the gradients are achieved by pumping the cations out of the cell, the plasma membrane potential enhances the leakage rate of these cations into the cell because of the orientation of the potential. This review proposes that cells use certain lipids to inhibit cation leakage through the membrane bilayers. It assumes that Na(+) leaks through the bilayer by a defect mechanism. For Na(+) leakage in animal plasma membranes, the evidence suggests that cholesterol is a key inhibitor of Na(+) leakage. Here I put forth a novel mechanism for proton leakage through lipid bilayers. The mechanism assumes water forms protonated and deprotonated clusters in the lipid bilayer. The model suggests how two features of lipid structures may inhibit H(+) leakage. One feature is the fused ring structure of sterols, hopanoids and tetrahymenol which extrude water and therefore clusters from the bilayer. The second feature is lipid structures that crowd the center of the bilayer with hydrocarbon. This can be accomplished either by separating the two monolayers with hydrocarbons such as isoprenes or isopranes in the bilayer's cleavage plane or by branching the lipid chains in the center of the bilayers with hydrocarbon. The natural distribution of lipids that contain these features are examined. Data in the literature shows that plasma membranes exposed to extreme concentrations of cations are particularly rich in the lipids containing the predicted qualities. Prokaryote plasma membranes that reside in extreme acids (acidophiles) contain both hopanoids and iso/anteiso- terminal lipid branching. Plasma membranes that reside in extreme base (alkaliphiles) contain both squalene and iso/anteiso- lipids. The mole fraction of squalene in alkaliphile bilayers increases, as they are cultured at higher pH. In eukaryotes, cation leak inhibition is here attributed to sterols and certain isoprenes, dolichol for lysosomes and peroxysomes, ubiquinone for these in addition to mitochondrion, and plastoquinone for the chloroplast. Phytosterols differ from cholesterol because they contain methyl and ethyl branches on the side chain. The proposal provides a structure-function rationale for distinguishing the structures of the phytosterols as inhibitors of proton leaks from that of cholesterol which is proposed to inhibit leaks of Na(+). The most extensively studied of sterols, cholesterol, occurs only in animal cells where there is a sodium gradient across the plasma membrane. In mammals, nearly 100 proteins participate in cholesterol's biosynthetic and degradation pathway, its regulatory mechanisms and cell-delivery system. Although a fat, cholesterol yields no energy on degradation. Experiments have shown that it reduces Na(+) and K(+) leakage through lipid bilayers to approximately one third of bilayers that lack the sterol. If sterols significantly inhibit cation leakage through the lipids of the plasma membrane, then the general role of all sterols is to save metabolic ATP energy, which is the penalty for cation leaks into the cytosol. The regulation of cholesterol's appearance in the plasma membrane and the evolution of sterols is discussed in light of this proposed role.

Effects of Lipid Composition on Bilayer Membranes Quantified by All-Atom Molecular Dynamics.

PubMed

Ding, Wei; Palaiokostas, Michail; Wang, Wen; Orsi, Mario

2015-12-10

Biological bilayer membranes typically contain varying amounts of lamellar and nonlamellar lipids. Lamellar lipids, such as dioleoylphosphatidylcholine (DOPC), are defined by their tendency to form the lamellar phase, ubiquitous in biology. Nonlamellar lipids, such as dioleoylphosphatidylethanolamine (DOPE), prefer instead to form nonlamellar phases, which are mostly nonbiological. However, nonlamellar lipids mix with lamellar lipids in biomembrane structures that remain overall lamellar. Importantly, changes in the lamellar vs nonlamellar lipid composition are believed to affect membrane function and modulate membrane proteins. In this work, we employ atomistic molecular dynamics simulations to quantify how a range of bilayer properties are altered by variations in the lamellar vs nonlamellar lipid composition. Specifically, we simulate five DOPC/DOPE bilayers at mixing ratios of 1/0, 3/1, 1/1, 1/3, and 0/1. We examine properties including lipid area and bilayer thickness, as well as the transmembrane profiles of electron density, lateral pressure, electric field, and dipole potential. While the bilayer structure is only marginally altered by lipid composition changes, dramatic effects are observed for the lateral pressure, electric field, and dipole potential profiles. Possible implications for membrane function are discussed.

Simulations of a Membrane-Anchored Peptide: Structure, Dynamics, and Influence on Bilayer Properties

PubMed Central

Jensen, Morten Ø.; Mouritsen, Ole G.; Peters, Günther H.

2004-01-01

A three-dimensional structure of a model decapeptide is obtained by performing molecular dynamics simulations of the peptide in explicit water. Interactions between an N-myristoylated form of the folded peptide anchored to dipalmitoylphosphatidylcholine fluid phase lipid membranes are studied at different applied surface tensions by molecular dynamics simulations. The lipid membrane environment influences the conformational space explored by the peptide. The overall secondary structure of the anchored peptide is found to deviate at times from its structure in aqueous solution through reversible conformational transitions. The peptide is, despite the anchor, highly mobile at the membrane surface with the peptide motion along the bilayer normal being integrated into the collective modes of the membrane. Peptide anchoring moderately alters the lateral compressibility of the bilayer by changing the equilibrium area of the membrane. Although membrane anchoring moderately affects the elastic properties of the bilayer, the model peptide studied here exhibits conformational flexibility and our results therefore suggest that peptide acylation is a feasible way to reinforce peptide-membrane interactions whereby, e.g., the lifetime of receptor-ligand interactions can be prolonged. PMID:15189854

An Investigation on bilayer structures of electrospun polyacrylonitrile nanofibrous membrane and cellulose membrane used as filtration media for apple juice clarification

NASA Astrophysics Data System (ADS)

Sawitri, Asti; Miftahul Munir, Muhammad; Edikresnha, Dhewa; Sandi, Ahzab; Fauzi, Ahmad; Rajak, Abdul; Natalia, Dessy; Khairurrijal, Khairurrijal

2018-05-01

Nanofibrous membrane has a potential to use in filtration technology with electrospinning as one of the techniques used in synthesizing nanofibers. Polyacrylonitrile (PAN) nanofibrous membranes with various fibers diameters were electrospun by varying its precursor solution concentration. The average fibers diameters of the PAN nanofibrous membranes obtained from the precursor solution concentrations of 6, 9, 12, and 14 wt% were 341, 534, 1274, and 2107 nm, respectively. Filtration media for apple juice clarification were bilayer-structured membranes made of PAN nanofibrous membranes on commercial cellulose microfibrous membranes. It has been shown that the reduction of apple juice color or turbidity performed by the cellulose microfibrous membrane was well enhanced by the presence of the PAN nanofibrous membrane in the bilayer-structured membrane. In addition, the apple-juice color and turbidity reductions increased with decreasing the average fibers diameter of the PAN nanofibrous membrane. Furthermore, the PAN nanofibrous membrane also helped the cellulose microfibrous membrane in the bilayer-structured membrane enhance the reductions of total phenols, protein, and glucose of the apple juice.

Formation of supported lipid bilayers containing phase-segregated domains and their interaction with gold nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Melby, Eric S.; Mensch, Arielle C.; Lohse, Samuel E.

2016-01-01

The cell membrane represents an important biological interface that nanoparticles may encounter after being released into the environment. Interaction of nanoparticles with cellular membranes may alter membrane structure and function, lead to their uptake into cells, and elicit adverse biological responses. Supported lipid bilayers have proven to be valuable ex vivo models for biological membranes, allowing investigation of their mechanisms of interaction with nanoparticles with a degree of control impossible in living cells. To date, the majority of research on nanoparticle interaction with supported lipid bilayers has employed membranes composed of single or binary mixtures of phospholipids. Cellular membranes containmore » a wide variety of lipids and exhibit lateral organization. Ordered membrane domains enriched in specific membrane components are referred to as lipid rafts and have not been explored with respect to their interaction with nanoparticles. Here we develop model lipid raft-containing membranes amenable to investigation by a variety of surface-sensitive analytical techniques and demonstrate that lipid rafts influence the extent of nanoparticle attachment to model membranes. We determined conditions that allow reliable formation of bilayers containing rafts enriched in sphingomyelin and cholesterol and confirmed their morphology by structured illumination and atomic force microscopies. We demonstrate that lipid rafts increase attachment of cationic gold nanoparticles to model membranes under near physiological ionic strength conditions (0.1 M NaCl) at pH 7.4. We anticipate that these results will serve as the foundation for and motivate further study of nanoparticle interaction with compositionally varied lipid rafts.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eicher, Barbara; Marquardt, Drew; Heberle, Frederick A.

We measured the effect of intrinsic lipid curvature, J 0, on structural properties of asymmetric vesicles made of palmitoyl-oleoyl-phosphatidylethanolamine (POPE; J 0 < 0) and palmitoyl-oleoyl-phosphatidylcholine (POPC; J 0 ~ 0). Electron microscopy and dynamic light scattering were used to determine vesicle size and morphology, and x-ray and neutron scattering, combined with calorimetric experiments and solution NMR, yielded insights into leaflet-specific lipid packing and melting processes. Below the lipid melting temperature we observed strong interleaflet coupling in asymmetric vesicles with POPE inner bilayer leaflets and outer leaflets enriched in POPC. This lipid arrangement manifested itself by lipids melting cooperatively inmore » both leaflets, and a rearrangement of lipid packing in both monolayers. On the other hand, no coupling was observed in vesicles with POPC inner bilayer leaflets and outer leaflets enriched in POPE. In this case, the leaflets melted independently and did not affect each other’s acyl chain packing. Furthermore, we found no evidence for transbilayer structural coupling above the melting temperature of either sample preparation. Our results are consistent with the energetically preferred location of POPE residing in the inner leaflet, where it also resides in natural membranes, most likely causing the coupling of both leaflets. The loss of this coupling in the fluid bilayers is most likely the result of entropic contributions.« less

Structure and interactions of fully hydrated dioleoylphosphatidylcholine bilayers.

PubMed Central

Tristram-Nagle, S; Petrache, H I; Nagle, J F

1998-01-01

This study focuses on dioleoylphosphatidylcholine (DOPC) bilayers near full hydration. Volumetric data and high-resolution synchrotron x-ray data are used in a method that compares DOPC with well determined gel phase dipalmitoylphosphatidylcholine (DPPC). The key structural quantity obtained is fully hydrated area/lipid A0 = 72.2 +/- 1.1 A2 at 30 degrees C, from which other quantities such as thickness of the bilayer are obtained. Data for samples over osmotic pressures from 0 to 56 atmospheres give an estimate for the area compressibility of KA = 188 dyn/cm. Obtaining the continuous scattering transform and electron density profiles requires correction for liquid crystal fluctuations. Quantitation of these fluctuations opens an experimental window on the fluctuation pressure, the primary repulsive interaction near full hydration. The fluctuation pressure decays exponentially with water spacing, in agreement with analytical results for soft confinement. However, the ratio of decay length lambda(fl) = 5.8 A to hydration pressure decay length lambda = 2.2 A is significantly larger than the value of 2 predicted by analytical theory and close to the ratio obtained in recent simulations. We also obtain the traditional osmotic pressure versus water spacing data. Our analysis of these data shows that estimates of the Hamaker parameter H and the bending modulus Kc are strongly coupled. PMID:9675192

Can NO-indomethacin counteract the topical gastric toxicity induced by indomethacin interactions with phospholipid bilayers?

PubMed

Pereira-Leite, Catarina; Nunes, Cláudia; Bozelli, José C; Schreier, Shirley; Kamma-Lorger, Christina S; Cuccovia, Iolanda M; Reis, Salette

2018-05-23

Nitric oxide (NO)-releasing nonsteroidal anti-inflammatory drugs (NSAIDs) have been developed to overcome the gastrointestinal and cardiovascular toxicity of NSAIDs, by chemically associating a NO-releasing moiety with commercial NSAIDs. Since increasing evidence supports that NSAIDs toxicity is related to their topical actions in membrane lipids, this work aims to evaluate the impact of adding a NO-releasing moiety to parent NSAIDs regarding their effect on lipid bilayers. Thus, the interactions of NO-indomethacin and indomethacin (parent drug) with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) bilayers were described herein at pH 3.0 and 7.4. Diverse experimental techniques were combined to characterize the partitioning and location of drugs in DMPC bilayers, and to analyze their effect on the lipid phase transition and the bilayer structure and dynamics. The partitioning of NO-indomethacin into DMPC bilayers was similar to that of charged indomethacin and smaller than that of neutral indomethacin. Both drugs were found to insert the DMPC bilayer and the membrane location of indomethacin was pH-dependent. NO-indomethacin and indomethacin induced a decrease of the main phase transition temperature of DMPC. The effect of these drugs on the bilayer structure and dynamics was dependent on diverse factors, namely drug ionization state, drug:lipid molar ratio, temperature and lipid phase. It is noteworthy that NO-indomethacin induced more pronounced alterations in the biophysical properties of DMPC bilayers than indomethacin, considering equivalent membrane concentrations. Such modifications may have in vivo implications, particularly in the gastric mucosa, where NO-NSAIDs-induced changes in the protective properties of phospholipid layers may contribute to the occurrence of adverse effects. Copyright © 2018 Elsevier B.V. All rights reserved.

Comparison of breaking tests for the characterization of the interfacial strength of bilayer tablets.

PubMed

Castrati, Luca; Mazel, Vincent; Busignies, Virginie; Diarra, Harona; Rossi, Alessandra; Colombo, Paolo; Tchoreloff, Pierre

2016-11-20

The bilayer tableting technology is gaining more acceptance in the drug industry, due to its ability to improve the drug delivery strategies. It is currently assessed by the European Pharmacopoeia, that the mechanical strength of tablets can be evaluated using a diametral breaking tester. This device applies a force diametrically, and records the tablet breaking point. This approach has been used to measure the structural integrity of single layer tablets as well as bilayer (and multi-layer) tablets. The latter ones, however, have a much complex structure. Therefore, testing a bilayer tablet with the currently used breaking test methodology might not be appropriate. The aim of this work was to compare results from several tests that have been proposed to quantify the interfacial strength of bilayer tablets. The obtained results would provide an indication on which tests are appropriate to evaluate the robustness of a bilayer tablet. Bilayer tablets were fabricated using a model formulation: Microcrystalline Cellulose (MCC) for the first layer, and spray dried lactose (SDLac) as second layer. Each set of tablets were tested using the following tests: Diametral Test, Shear Test and Indentation Test. The tablets were examined before and after the breaking test using Scanning Electron Microscopy (SEM). When a bilayer tablet was subjected to shearing or indentation, it showed signs of clear delamination. Differently, using the diametral test system, the tablets showed no clear difference, before and after the testing. However, when examining each layer via SEM, it was clear that a fracture occurred in the layer made of SDLac. Thus, the diametral test is a measure of the strength of one of the two layers and therefore it is not suited to test the mechanical strength of bilayer tablets. Copyright © 2016 Elsevier B.V. All rights reserved.

Multilayer composites and manufacture of same

DOEpatents

Holesinger, Terry G.; Jia, Quanxi

2006-02-07

The present invention is directed towards a process of depositing multilayer thin films, disk-shaped targets for deposition of multilayer thin films by a pulsed laser or pulsed electron beam deposition process, where the disk-shaped targets include at least two segments with differing compositions, and a multilayer thin film structure having alternating layers of a first composition and a second composition, a pair of the alternating layers defining a bi-layer wherein the thin film structure includes at least 20 bi-layers per micron of thin film such that an individual bi-layer has a thickness of less than about 100 nanometers.

Solid oxide fuel cells with bi-layered electrolyte structure

NASA Astrophysics Data System (ADS)

Zhang, Xinge; Robertson, Mark; Decès-Petit, Cyrille; Xie, Yongsong; Hui, Rob; Qu, Wei; Kesler, Olivera; Maric, Radenka; Ghosh, Dave

In this work, we have developed solid oxide fuel cells with a bi-layered electrolyte of 2 μm SSZ and 4 μm SDC using tape casting, screen printing, and co-firing processes. The cell reached power densities of 0.54 W cm -2 at 650 °C and 0.85 W cm -2 at 700 °C, with open circuit voltage (OCV) values larger than 1.02 V. The electrical leaking between anode and cathode through an SDC electrolyte has been blocked in the bi-layered electrolyte structure. However, both the electrolyte resistance (R el) and electrode polarization resistance (R p,a+c) increased in comparison to cells with single-layered SDC electrolytes. The formation of a solid solution of (Ce, Zr)O 2- x during sintering process and the flaws in the bi-layered electrolyte structure seem to be the main causes for the increase in the R el value (0.32 Ω cm 2) at 650 °C, which is almost one order of magnitude higher than the calculated value.

The partition and transport behavior of cytotoxic ionic liquids (ILs) through the DPPC bilayer: Insights from molecular dynamics simulation.

PubMed

Ganjali Koli, Mokhtar; Azizi, Khaled

A molecular dynamics (MD) simulation with atomistic details was performed to examine the partitioning and transport behavior of moderately cytotoxic ionic liquids (ILs), namely choline bis(2-ethylhexyl) phosphate (CBEH), choline bis(2,4,4-trimethylpentyl) phosphinate (CTMP) and choline O,O-diethyl dithiophosphate (CDEP) in a fully hydrated dipalmitoylphosphatidylcholine (DPPC) bilayer in the fluid phase at 323 K. The structure of ILs was so selected to understand if the role of dipole and dispersion forces in the ILs distribution in the membrane can be possible. Several analyses including mass density, electrostatic potential, order parameter, diffusion coefficients and hydrogen bond formation, was carried out to determine the precise location of the anionic species inside the membrane. Moreover, the potential of the mean force (PMF) method was used to calculate free energy profile for transferring anionic species from the DPPC membrane into the bulk water. While less cytotoxic DEP is located within the bulk water, more cytotoxic TMP and BEH ILs were found to remain in the membrane and the energy barrier for crossing through the bilayer center of BEH was higher. Various ILs have no significant effect on P-N vector. The thickness of lipid bilayer decreased in all systems comprising ILs, while area per lipid increased.

Structure and dynamics of water and lipid molecules in charged anionic DMPG lipid bilayer membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rønnest, A. K.; Peters, G. H.; Hansen, F. Y., E-mail: flemming@kemi.dtu.dk

2016-04-14

Molecular dynamics simulations have been used to investigate the influence of the valency of counter-ions on the structure of freestanding bilayer membranes of the anionic 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) lipid at 310 K and 1 atm. At this temperature, the membrane is in the fluid phase with a monovalent counter-ion and in the gel phase with a divalent counter-ion. The diffusion constant of water as a function of its depth in the membrane has been determined from mean-square-displacement calculations. Also, calculated incoherent quasielastic neutron scattering functions have been compared to experimental results and used to determine an average diffusion constant for allmore » water molecules in the system. On extrapolating the diffusion constants inferred experimentally to a temperature of 310 K, reasonable agreement with the simulations is obtained. However, the experiments do not have the sensitivity to confirm the diffusion of a small component of water bound to the lipids as found in the simulations. In addition, the orientation of the dipole moment of the water molecules has been determined as a function of their depth in the membrane. Previous indirect estimates of the electrostatic potential within phospholipid membranes imply an enormous electric field of 10{sup 8}–10{sup 9} V m{sup −1}, which is likely to have great significance in controlling the conformation of translocating membrane proteins and in the transfer of ions and molecules across the membrane. We have calculated the membrane potential for DMPG bilayers and found ∼1 V (∼2 ⋅ 10{sup 8} V m{sup −1}) when in the fluid phase with a monovalent counter-ion and ∼1.4 V (∼2.8 ⋅ 10{sup 8} V m{sup −1}) when in the gel phase with a divalent counter-ion. The number of water molecules for a fully hydrated DMPG membrane has been estimated to be 9.7 molecules per lipid in the gel phase and 17.5 molecules in the fluid phase, considerably smaller than inferred experimentally for 1,2-dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC) membranes but comparable to the number inferred for 1,2-dilauroyl-sn-glycero-3-phosphoethanolamine (DLPE) membranes. Some of the properties of the DMPG membrane are compared with those of the neutral zwitterionic DMPC bilayer membrane at 303 K and 1 atm, which is the same reduced temperature with respect to the gel-to-fluid transition temperature as 310 K is for the DMPG bilayer membrane.« less

Subnanometer structure of an asymmetric model membrane: Interleaflet coupling influences domain properties

DOE PAGES

Heberle, Frederick A.; Marquardt, Drew; Doktorova, Milka; ...

2016-04-29

Cell membranes possess a complex three-dimensional architecture, including nonrandom lipid lateral organization within the plane of a bilayer leaflet, and compositional asymmetry between the two leaflets. As a result, delineating the membrane structure–function relationship has been a highly challenging task. Even in simplified model systems, the interactions between bilayer leaflets are poorly understood, due in part to the difficulty of preparing asymmetric model membranes that are free from the effects of residual organic solvent or osmotic stress. To address these problems, we have modified a technique for preparing asymmetric large unilamellar vesicles (aLUVs) via cyclodextrin-mediated lipid exchange in order tomore » produce tensionless, solvent-free aLUVs suitable for a range of biophysical studies. Leaflet composition and structure were characterized using isotopic labeling strategies, which allowed us to avoid the use of bulky labels. NMR and gas chromatography provided precise quantification of the extent of lipid exchange and bilayer asymmetry, while small-angle neutron scattering (SANS) was used to resolve bilayer structural features with subnanometer resolution. Isotopically asymmetric POPC vesicles were found to have the same bilayer thickness and area per lipid as symmetric POPC vesicles, demonstrating that the modified exchange protocol preserves native bilayer structure. Partial exchange of DPPC into the outer leaflet of POPC vesicles produced chemically asymmetric vesicles with a gel/fluid phase-separated outer leaflet and a uniform, POPC-rich inner leaflet. SANS was able to separately resolve the thicknesses and areas per lipid of coexisting domains, revealing reduced lipid packing density of the outer leaflet DPPC-rich phase compared to typical gel phases. Lastly, our finding that a disordered inner leaflet can partially fluidize ordered outer leaflet domains indicates some degree of interleaflet coupling, and invites speculation on a role for bilayer asymmetry in modulating membrane lateral organization.« less

Cardiolipin effects on membrane structure and dynamics.

PubMed

Unsay, Joseph D; Cosentino, Katia; Subburaj, Yamunadevi; García-Sáez, Ana J

2013-12-23

Cardiolipin (CL) is a lipid with unique properties solely found in membranes generating electrochemical potential. It contains four acyl chains and tends to form nonlamellar structures, which are believed to play a key role in membrane structure and function. Indeed, CL alterations have been linked to disorders such as Barth syndrome and Parkinson's disease. However, the molecular effects of CL on membrane organization remain poorly understood. Here, we investigated the structure and physical properties of CL-containing membranes using confocal microscopy, fluorescence correlation spectroscopy, and atomic force microscopy. We found that the fluidity of the lipid bilayer increased and its mechanical stability decreased with CL concentration, indicating that CL decreases the packing of the membrane. Although the presence of up to 20% CL gave rise to flat, stable bilayers, the inclusion of 5% CL promoted the formation of flowerlike domains that grew with time. Surprisingly, we often observed two membrane-piercing events in atomic force spectroscopy experiments with CL-containing membranes. Similar behavior was observed with a lipid mixture mimicking the mitochondrial outer membrane composition. This suggests that CL promotes the formation of membrane areas with apposed double bilayers or nonlamellar structures, similar to those proposed for mitochondrial contact sites. All together, we show that CL induces membrane alterations that support the role of CL in facilitating bilayer structure remodeling, deformation, and permeabilization.

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

Energetic and dynamic analysis of transport of Na + and K + through a cyclic peptide nanotube in water and in lipid bilayers

DOE PAGES

Song, Yeonho; Lee, Ji Hye; Hwang, Hoon; ...

2016-11-04

Potential of mean force (PMF) profiles and position-dependent diffusion coefficients of Na + and K + are calculated to elucidate the translocation of ions through a cyclic peptide nanotube, composed of 8 × cyclo[-(D-Leu-Trp) 4-] rings, in water and in hydrated DMPC bilayers. The PMF profiles and PMF decomposition analysis for the monovalent cations show that favorable interactions of the cations with the CPN as well as the lipid bilayer and dehydration free energy penalties are two major competing factors which determine the free energy surface for ion transport through CPNs both in water and lipid bilayers, and that themore » selectivity of CPNs to cations mainly arises from favorable interaction energies of cations with CPNs and lipid bilayers that are more dominant than the dehydration penalties. Calculations of the position-dependent diffusion coefficients and dynamic friction kernels of the cations indicate that the dehydration process along with the molecular rearrangements occurring outside the channel and the coupling of the ion motions with the chain-structured water movements inside the channel lead to decrease of the diffusion coefficients far away from the channel entrance and also reduced coefficients inside the channel. Here the PMF and diffusivity profiles for Na + and K + reveal that the energetics of ion transport through the CPN are governed by global interactions of ions with all the components in the system while the diffusivity of ions through the channel is mostly determined by local interactions of ions with the confined water molecules inside the channel. Comparison of Na + and K + ion distributions based on overdamped Brownian dynamics simulations based on the PMF and diffusivity profiles with the corresponding results from molecular dynamics shows good agreement, indicating accuracy of the Bayesian inference method for determining diffusion coefficients in this application. In addition this work shows that position-dependent diffusion coefficients of ions are required to explain the dynamics and conductance of ions through the CPN properly.« less

Specific Binding of Adamantane Drugs and Direction of their Polar Amines in the Pore of the Influenza M2 Transmembrane Domain in Lipid Bilayers and Dodecylphosphocholine Micelles Determined by NMR Spectroscopy

PubMed Central

Cady, Sarah D.; Wang, Jun; Wu, Yibing; DeGrado, William F.; Hong, Mei

2011-01-01

The transmembrane domain of the influenza M2 protein (M2TM) forms a tetrameric proton channel important for the virus lifecycle. The proton-channel activity is inhibited by amine-containing adamantyl drugs amantadine and rimantadine, which have been shown to bind specifically to the pore of M2TM near Ser31. However, whether the polar amine points to the N- or C-terminus of the channel has not yet been determined. Elucidating the polar group direction will shed light on the mechanism by which drug binding inhibits this proton channel and will facilitate rational design of new inhibitors. In this study, we determine the polar amine direction using M2TM reconstituted in lipid bilayers as well as DPC micelles. 13C-2H rotational-echo double-resonance NMR experiments of 13C-labeled M2TM and methyl-deuterated rimantadine in lipid bilayers showed that the polar amine pointed to the C-terminus of the channel, with the methyl group close to Gly34. Solution NMR experiments of M2TM in dodecylphosphocholine (DPC) micelles indicate that drug binding causes significant chemical shift perturbations of the protein that are very similar to those seen for M2TM and M2(18–60) bound to lipid bilayers. Specific 2H-labeling of the drugs permitted the assignment of drug-protein cross peaks, which indicate that amantadine and rimantadine bind to the pore in the same fashion as for bilayer-bound M2TM. These results strongly suggest that adamantyl inhibition of M2TM is achieved not only by direct physical occlusion of the pore but also by perturbing the equilibrium constant of the proton-sensing residue His37. The reproduction of the pharmacologically relevant specific pore-binding site in DPC micelles, which was not observed with a different detergent, DHPC, underscores the significant influence of the detergent environment on the functional structure of membrane proteins. PMID:21381693

Structure of Immune Stimulating Complex Matrices and Immune Stimulating Complexes in Suspension Determined by Small-Angle X-Ray Scattering

PubMed Central

Pedersen, Jan Skov; Oliveira, Cristiano L.P.; Hübschmann, Henriette Baun; Arleth, Lise; Manniche, Søren; Kirkby, Nicolai; Nielsen, Hanne Mørck

2012-01-01

Immune stimulating complex (ISCOM) particles consisting of a mixture of Quil-A, cholesterol, and phospholipids were structurally characterized by small-angle x-ray scattering (SAXS). The ISCOM particles are perforated vesicles of very well-defined structures. We developed and implemented a novel (to our knowledge) modeling method based on Monte Carlo simulation integrations to describe the SAXS data. This approach is similar to the traditional modeling of SAXS data, in which a structure is assumed, the scattering intensity is calculated, and structural parameters are optimized by weighted least-squares methods when the model scattering intensity is fitted to the experimental data. SAXS data from plain ISCOM matrix particles in aqueous suspension, as well as those from complete ISCOMs (i.e., with an antigen (tetanus toxoid) incorporated) can be modeled as a polydisperse distribution of perforated bilayer vesicles with icosahedral, football, or tennis ball structures. The dominating structure is the tennis ball structure, with an outer diameter of 40 nm and with 20 holes 5–6 nm in diameter. The lipid bilayer membrane is 4.6 nm thick, with a low-electron-density, 2.0-nm-thick hydrocarbon core. Surprisingly, in the ISCOMs, the tetanus toxoid is located just below the membrane inside the particles. PMID:22677391

Convergence of Free Energy Profile of Coumarin in Lipid Bilayer

PubMed Central

2012-01-01

Atomistic molecular dynamics (MD) simulations of druglike molecules embedded in lipid bilayers are of considerable interest as models for drug penetration and positioning in biological membranes. Here we analyze partitioning of coumarin in dioleoylphosphatidylcholine (DOPC) bilayer, based on both multiple, unbiased 3 μs MD simulations (total length) and free energy profiles along the bilayer normal calculated by biased MD simulations (∼7 μs in total). The convergences in time of free energy profiles calculated by both umbrella sampling and z-constraint techniques are thoroughly analyzed. Two sets of starting structures are also considered, one from unbiased MD simulation and the other from “pulling” coumarin along the bilayer normal. The structures obtained by pulling simulation contain water defects on the lipid bilayer surface, while those acquired from unbiased simulation have no membrane defects. The free energy profiles converge more rapidly when starting frames from unbiased simulations are used. In addition, z-constraint simulation leads to more rapid convergence than umbrella sampling, due to quicker relaxation of membrane defects. Furthermore, we show that the choice of RESP, PRODRG, or Mulliken charges considerably affects the resulting free energy profile of our model drug along the bilayer normal. We recommend using z-constraint biased MD simulations based on starting geometries acquired from unbiased MD simulations for efficient calculation of convergent free energy profiles of druglike molecules along bilayer normals. The calculation of free energy profile should start with an unbiased simulation, though the polar molecules might need a slow pulling afterward. Results obtained with the recommended simulation protocol agree well with available experimental data for two coumarin derivatives. PMID:22545027

Convergence of Free Energy Profile of Coumarin in Lipid Bilayer.

PubMed

Paloncýová, Markéta; Berka, Karel; Otyepka, Michal

2012-04-10

Atomistic molecular dynamics (MD) simulations of druglike molecules embedded in lipid bilayers are of considerable interest as models for drug penetration and positioning in biological membranes. Here we analyze partitioning of coumarin in dioleoylphosphatidylcholine (DOPC) bilayer, based on both multiple, unbiased 3 μs MD simulations (total length) and free energy profiles along the bilayer normal calculated by biased MD simulations (∼7 μs in total). The convergences in time of free energy profiles calculated by both umbrella sampling and z-constraint techniques are thoroughly analyzed. Two sets of starting structures are also considered, one from unbiased MD simulation and the other from "pulling" coumarin along the bilayer normal. The structures obtained by pulling simulation contain water defects on the lipid bilayer surface, while those acquired from unbiased simulation have no membrane defects. The free energy profiles converge more rapidly when starting frames from unbiased simulations are used. In addition, z-constraint simulation leads to more rapid convergence than umbrella sampling, due to quicker relaxation of membrane defects. Furthermore, we show that the choice of RESP, PRODRG, or Mulliken charges considerably affects the resulting free energy profile of our model drug along the bilayer normal. We recommend using z-constraint biased MD simulations based on starting geometries acquired from unbiased MD simulations for efficient calculation of convergent free energy profiles of druglike molecules along bilayer normals. The calculation of free energy profile should start with an unbiased simulation, though the polar molecules might need a slow pulling afterward. Results obtained with the recommended simulation protocol agree well with available experimental data for two coumarin derivatives.

Multiscale simulations on conformational dynamics and membrane interactions of the non-structural 2 (NS2) transmembrane domain.

PubMed

Hung, Huynh Minh; Hang, Tran Dieu; Nguyen, Minh Tho

2016-09-09

Hepatitis C virus (HCV) is one of the most crucial global health issues, in which the HCV non-structural protein 2 (NS2), particularly its three transmembrane segments, plays a crucial role in HCV assembly. In this context, multiscale MD simulations have been applied to investigate the preferred orientation of transmembrane domain of NS2 protein (TNS2) in a POPC bilayer, structural stability and characteristic of intramembrane protein-lipid and protein-protein interaction. Our study indicates that NS2 protein adopts three trans-membrane segments with highly stable α-helix structure in a POPC bilayer and a short helical luminal segment. While the first and second TM segment involved in continuous helical domain, the third TM segment is however cleaved into two sub-segments with different tilt angles via a kink at L87G88. Salt bridges K81-E45, R32-PO4 and R43-PO4 are determined as the key factor to stabilize the structure of TM2 and TM3 which consist of charged residues located in the hydrophobic region of the membrane. Copyright © 2016 Elsevier Inc. All rights reserved.

Thermoelastic damping in bilayered microbar resonators with circular cross-section

NASA Astrophysics Data System (ADS)

Liang, Xiaoyao; Li, Pu

2017-11-01

It is always a challenge to determine the Thermoelastic damping (TED) in bilayered microbars precisely. In this paper, a model for TED in the bilayered and cantilevered microbar was proposed, in which the total damping was derived by calculating the energy evanished in each layer. The distribution of temperature in the bilayered microbar with a thermodynamically ideal boundary receiving a time-harmonic force is obtained. An infinite summation for the computing of TED in the bilayered slender microbars under axial loading is presented, and the convergence rate of it is discussed. There are little differences between the results computed by our model and that by finite element method (FEM).

Potassium-doped n-type bilayer graphene

NASA Astrophysics Data System (ADS)

Yamada, Takatoshi; Okigawa, Yuki; Hasegawa, Masataka

2018-01-01

Potassium-doped n-type bilayer graphene was obtained. Chemical vapor deposited bilayer and single layer graphene on copper (Cu) foils were used. After etching of Cu foils, graphene was dipped in potassium hydroxide aqueous solutions to dope potassium. Graphene on silicon oxide was characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and Raman spectroscopy. Both XPS and EDX spectra indicated potassium incorporation into the bilayer graphene via intercalation between the graphene sheets. The downward shift of the 2D peak position of bilayer graphene after the potassium hydroxide (KOH) treatment was confirmed in Raman spectra, indicating that the KOH-treated bilayer graphene was doped with electrons. Electrical properties were measured using Hall bar structures. The Dirac points of bilayer graphene were shifted from positive to negative by the KOH treatment, indicating that the KOH-treated bilayer graphene was n-type conduction. For single layer graphene after the KOH treatment, although electron doping was confirmed from Raman spectra, the peak of potassium in the X-ray photoelectron spectroscopy (XPS) spectrum was not detected. The Dirac points of single layer graphene with and without the KOH treatment showed positive.

Assessment of bilayer silicene to probe as quantum spin and valley Hall effect

NASA Astrophysics Data System (ADS)

Rehman, Majeed Ur; Qiao, Zhenhua

2018-02-01

Silicene takes precedence over graphene due to its buckling type structure and strong spin orbit coupling. Motivated by these properties, we study the silicene bilayer in the presence of applied perpendicular electric field and intrinsic spin orbit coupling to probe as quantum spin/valley Hall effect. Using analytical approach, we calculate the spin Chern-number of bilayer silicene and then compare it with monolayer silicene. We reveal that bilayer silicene hosts double spin Chern-number as compared to single layer silicene and therefore accordingly has twice as many edge states in contrast to single layer silicene. In addition, we investigate the combined effect of intrinsic spin orbit coupling and the external electric field, we find that bilayer silicene, likewise single layer silicene, goes through a phase transitions from a quantum spin Hall state to a quantum valley Hall state when the strength of the applied electric field exceeds the intrinsic spin orbit coupling strength. We believe that the results and outcomes obtained for bilayer silicene are experimentally more accessible as compared to bilayer graphene, because of strong SO coupling in bilayer silicene.

Structure and functions of simple membrane-water interfaces. [Abstract only

NASA Technical Reports Server (NTRS)

Pohorille, A.; Wilson, M. A.

1994-01-01

The structure and functions of the earliest ancestors of contemporary cells are focal points in studies of the origin of life. Probably the first cell-like structures were vesicles - closed, spheroidal structures with aqueous medium trapped inside. The membranous walls of vesicles were most likely bilayers composed of simple amphiphilic material available on early earth. The membrane studied was composed of glycerol 1-monooleate (GMO). Glycerol forms the polar head group and the oily tail contains 18 carbon atoms. All head groups have been found to be located in two narrow regions at the interfaces with water. The membrane interior, formed by the hydrophobic tails, is quite fluid with chain disorder increasing towards the center of the bilayer. These results are in agreement with x-ray and neutron scattering data from related bilayers. The width of the membrane is not constant, but fluctuates in time and space. Occasional thinning defects in the membrane, observed during the course of the simulations, may have a significant influence on rates of passive transport of small molecules across membranes. It has been found that water penetrates the head group region but not the oily interior of the membrane. Water molecules near the interface are oriented by dipoles of the head groups. The resulting electrostatic potential across the interface, determined in our simulations, has been found to be markedly larger than across the water-oil interface. This quantity has been implicated as the source of selectivity, with respect to the sign of the charge, as an ion approaches the interface and during transport of hydrophobic ions across membranes.

Initial Steps of Rubicene Film Growth on Silicon Dioxide.

PubMed

Scherwitzl, Boris; Lukesch, Walter; Hirzer, Andreas; Albering, Jörg; Leising, Günther; Resel, Roland; Winkler, Adolf

2013-02-28

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV.

Initial Steps of Rubicene Film Growth on Silicon Dioxide

PubMed Central

2013-01-01

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV. PMID:23476720

Surface functionalization of a polymeric lipid bilayer for coupling a model biological membrane with molecules, cells, and microstructures.

PubMed

Morigaki, Kenichi; Mizutani, Kazuyuki; Saito, Makoto; Okazaki, Takashi; Nakajima, Yoshihiro; Tatsu, Yoshiro; Imaishi, Hiromasa

2013-02-26

We describe a stable and functional model biological membrane based on a polymerized lipid bilayer with a chemically modified surface. A polymerized lipid bilayer was formed from a mixture of two diacetylene-containing phospholipids, 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DiynePC) and 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphoethanolamine (DiynePE). DiynePC formed a stable bilayer structure, whereas the ethanolamine headgroup of DiynePE enabled functional molecules to be grafted onto the membrane surface. Copolymerization of DiynePC and DiynePE resulted in a robust bilayer. Functionalization of the polymeric bilayer provided a route to a robust and biomimetic surface that can be linked with biomolecules, cells, and three-dimensional (3D) microstructures. Biotin and peptides were grafted onto the polymeric bilayer for attaching streptavidin and cultured mammalian cells by molecular recognition, respectively. Nonspecific adsorption of proteins and cells on polymeric bilayers was minimum. DiynePE was also used to attach a microstructure made of an elastomer (polydimethylsiloxan: PDMS) onto the membrane, forming a confined aqueous solution between the two surfaces. The microcompartment enabled us to assay the activity of a membrane-bound enzyme (cyochrome P450). Natural (fluid) lipid bilayers were incorporated together with membrane-bound proteins by lithographically polymerizing DiynePC/DiynePE bilayers. The hybrid membrane of functionalized polymeric bilayers and fluid bilayers offers a novel platform for a wide range of biomedical applications including biosensor, bioassay, cell culture, and cell-based assay.

High-resolution orientation and depth of insertion of the voltage-sensing S4 helix of a potassium channel in lipid bilayers.

PubMed

Doherty, Tim; Su, Yongchao; Hong, Mei

2010-08-27

The opening and closing of voltage-gated potassium (Kv) channels are controlled by several conserved Arg residues in the S4 helix of the voltage-sensing domain. The interaction of these positively charged Arg residues with the lipid membrane has been of intense interest for understanding how membrane proteins fold to allow charged residues to insert into lipid bilayers against free-energy barriers. Using solid-state NMR, we have now determined the orientation and insertion depth of the S4 peptide of the KvAP channel in lipid bilayers. Two-dimensional (15)N correlation experiments of macroscopically oriented S4 peptide in phospholipid bilayers revealed a tilt angle of 40 degrees and two possible rotation angles differing by 180 degrees around the helix axis. Remarkably, the tilt angle and one of the two rotation angles are identical to those of the S4 helix in the intact voltage-sensing domain, suggesting that interactions between the S4 segment and other helices of the voltage-sensing domain are not essential for the membrane topology of the S4 helix. (13)C-(31)P distances between the S4 backbone and the lipid (31)P indicate a approximately 9 A local thinning and 2 A average thinning of the DMPC (1,2-dimyristoyl-sn-glycero-3-phosphochloline)/DMPG (1,2-dimyristoyl-sn-glycero-3-phosphatidylglycerol) bilayer, consistent with neutron diffraction data. Moreover, a short distance of 4.6 A from the guanidinium C(zeta) of the second Arg to (31)P indicates the existence of guanidinium phosphate hydrogen bonding and salt bridges. These data suggest that the structure of the Kv gating helix is mainly determined by protein-lipid interactions instead of interhelical protein-protein interactions, and the S4 amino acid sequence encodes sufficient information for the membrane topology of this crucial gating helix. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Lipid nanotechnologies for structural studies of membrane-associated proteins.

PubMed

Stoilova-McPhie, Svetla; Grushin, Kirill; Dalm, Daniela; Miller, Jaimy

2014-11-01

We present a methodology of lipid nanotubes (LNT) and nanodisks technologies optimized in our laboratory for structural studies of membrane-associated proteins at close to physiological conditions. The application of these lipid nanotechnologies for structure determination by cryo-electron microscopy (cryo-EM) is fundamental for understanding and modulating their function. The LNTs in our studies are single bilayer galactosylceramide based nanotubes of ∼20 nm inner diameter and a few microns in length, that self-assemble in aqueous solutions. The lipid nanodisks (NDs) are self-assembled discoid lipid bilayers of ∼10 nm diameter, which are stabilized in aqueous solutions by a belt of amphipathic helical scaffold proteins. By combining LNT and ND technologies, we can examine structurally how the membrane curvature and lipid composition modulates the function of the membrane-associated proteins. As proof of principle, we have engineered these lipid nanotechnologies to mimic the activated platelet's phosphtaidylserine rich membrane and have successfully assembled functional membrane-bound coagulation factor VIII in vitro for structure determination by cryo-EM. The macromolecular organization of the proteins bound to ND and LNT are further defined by fitting the known atomic structures within the calculated three-dimensional maps. The combination of LNT and ND technologies offers a means to control the design and assembly of a wide range of functional membrane-associated proteins and complexes for structural studies by cryo-EM. The presented results confirm the suitability of the developed methodology for studying the functional structure of membrane-associated proteins, such as the coagulation factors, at a close to physiological environment. © 2014 Wiley Periodicals, Inc.

Performance Enhancement of Small Molecular Solar Cells by Bilayer Cathode Buffer.

PubMed

Sun, Qinjun; Zhao, Huanbin; Zhou, Miao; Gao, Liyan; Hao, Yuying

2016-04-01

An effective composite bilayer cathode buffer structure is proposed for use in small molecular solar cells. CsF was doped in Alq3 to form the first cathode buffer, leading to small serial resistances. BCP was used as the second cathode buffer to block the holes to the electrode. The optimized bilayer cathode buffer significantly increased the short circuit and fill factor of devices. By integrating this bilayer cathode buffer, the CuPc/C60 small molecular heterojunction cell exhibited a power conversion efficiency of up to 0.8%, which was an improvement of 56% compared to a device with only the Alq3 cathode buffer. Meanwhile, the bilayer cathode buffer still has a good protective effect on the performance of the device.

Electrical and structural characterization of plasma polymerized polyaniline/TiO2 heterostructure diode: a comparative study of single and bilayer TiO2 thin film electrode.

PubMed

Ameen, Sadia; Akhtar, M Shaheer; Kimi, Young Soon; Yang, O-Bong; Shin, Hyung-Shik

2011-04-01

A heterostructure was fabricated using p-type plasma polymerized polyaniline (PANI) and n-type (single and bilayer) titanium dioxide (TiO2) thin film on FTO glass. The deposition of single and bilayer TiO2 thin film on FTO substrate was achieved through doctor blade followed by dip coating technique before subjected to plasma enhanced polymerization. To fabricate p-n heterostructure, a plasma polymerization of aniline was conducted using RF plasma at 13.5 MHz and at the power of 120 W on the single and bilayer TiO2 thin film electrodes. The morphological, optical and the structural characterizations revealed the formation of p-n heterostructures between PANI and TiO2 thin film. The PANI/bilayer TiO2 heterostructure showed the improved current-voltage (I-V) characteristics due to the substantial deposition of PANI molecules into the bilayer TiO2 thin film which provided good conducting pathway and reduced the degree of excitons recombination. The change of linear I-V behavior of PANI/TiO2 heterostructure to non linear behavior with top Pt contact layer confirmed the formation of Schottky contact at the interfaces of Pt layer and PANI/TiO2 thin film layers.

How does ytterbium chloride interact with DMPC bilayers? A computational and experimental study.

PubMed

Gonzalez, Miguel A; Barriga, Hanna M G; Richens, Joanna L; Law, Robert V; O'Shea, Paul; Bresme, Fernando

2017-03-29

Lanthanide salts have been studied for many years, primarily in Nuclear Magnetic Resonance (NMR) experiments of mixed lipid-protein systems and more recently to study lipid flip-flop in model membrane systems. It is well recognised that lanthanide salts can influence the behaviour of both lipid and protein systems, however a full molecular level description of lipid-lanthanide interactions is still outstanding. Here we present a study of lanthanide-bilayer interactions, using molecular dynamics computer simulations, fluorescence electrostatic potential experiments and nuclear magnetic resonance. Computer simulations reveal the microscopic structure of DMPC lipid bilayers in the presence of Yb 3+ , and a surprising ability of the membranes to adsorb significant concentrations of Yb 3+ without disrupting the overall membrane structure. At concentrations commonly used in NMR experiments, Yb 3+ ions bind strongly to 5 lipids, inducing a small decrease of the area per lipid and a slight increase of the ordering of the aliphatic chains and the bilayer thickness. The area compressibility modulus increases by a factor of two, with respect to the free-salt case, showing that Yb 3+ ions make the bilayer more rigid. These modifications of the bilayer properties should be taken into account in the interpretation of NMR experiments.

Low operational current spin Hall nano-oscillators based on NiFe/W bilayers

NASA Astrophysics Data System (ADS)

Mazraati, Hamid; Chung, Sunjae; Houshang, Afshin; Dvornik, Mykola; Piazza, Luca; Qejvanaj, Fatjon; Jiang, Sheng; Le, Tuan Q.; Weissenrieder, Jonas; Åkerman, Johan

2016-12-01

We demonstrate highly efficient spin Hall nano-oscillators (SHNOs) based on NiFe/β-W bilayers. Thanks to the very high spin Hall angle of β-W, we achieve more than a 60% reduction in the auto-oscillation threshold current compared to NiFe/Pt bilayers. The structural, electrical, and magnetic properties of the bilayers, as well as the microwave signal generation properties of the SHNOs, have been studied in detail. Our results provide a promising path for the realization of low-current SHNO microwave devices with highly efficient spin-orbit torque from β-W.

Interfacial Structure and Chemistry of GaN on Ge(111)

NASA Astrophysics Data System (ADS)

Zhang, Siyuan; Zhang, Yucheng; Cui, Ying; Freysoldt, Christoph; Neugebauer, Jörg; Lieten, Ruben R.; Barnard, Jonathan S.; Humphreys, Colin J.

2013-12-01

The interface of GaN grown on Ge(111) by plasma-assisted molecular beam epitaxy is resolved by aberration corrected scanning transmission electron microscopy. A novel interfacial structure with a 5∶4 closely spaced atomic bilayer is observed that explains why the interface is flat, crystalline, and free of GeNx. Density functional theory based total energy calculations show that the interface bilayer contains Ge and Ga atoms, with no N atoms. The 5∶4 bilayer at the interface has a lower energy than a direct stacking of GaN on Ge(111) and enables the 5∶4 lattice-matching growth of GaN.

Enhanced Circular Dichroism of Gold Bilayered Slit Arrays Embedded with Rectangular Holes.

PubMed

Zhang, Hao; Wang, Yongkai; Luo, Lina; Wang, Haiqing; Zhang, Zhongyue

2017-01-01

Gold bilayered slit arrays with rectangular holes embedded into the metal surface are designed to enhance the circular dichroism (CD) effect of gold bilayered slit arrays. The rectangular holes in these arrays block electric currents and generate localized surface plasmons around these holes, thereby strengthening the CD effect. The CD enhancement factor depends strongly on the rotational angle and the structural parameters of the rectangular holes; this factor can be enhanced further by drilling two additional rectangular holes into the metal surfaces of the arrays. These results help facilitate the design of chiral structures to produce a strong CD effect and large electric fields.

Strain solitons and topological defects in bilayer graphene

PubMed Central

Alden, Jonathan S.; Tsen, Adam W.; Huang, Pinshane Y.; Hovden, Robert; Brown, Lola; Park, Jiwoong; Muller, David A.; McEuen, Paul L.

2013-01-01

Bilayer graphene has been a subject of intense study in recent years. The interlayer registry between the layers can have dramatic effects on the electronic properties: for example, in the presence of a perpendicular electric field, a band gap appears in the electronic spectrum of so-called Bernal-stacked graphene [Oostinga JB, et al. (2007) Nature Materials 7:151–157]. This band gap is intimately tied to a structural spontaneous symmetry breaking in bilayer graphene, where one of the graphene layers shifts by an atomic spacing with respect to the other. This shift can happen in multiple directions, resulting in multiple stacking domains with soliton-like structural boundaries between them. Theorists have recently proposed that novel electronic states exist at these boundaries [Vaezi A, et al. (2013) arXiv:1301.1690; Zhang F, et al. (2013) arXiv:1301.4205], but very little is known about their structural properties. Here we use electron microscopy to measure with nanoscale and atomic resolution the widths, motion, and topological structure of soliton boundaries and related topological defects in bilayer graphene. We find that each soliton consists of an atomic-scale registry shift between the two graphene layers occurring over 6–11 nm. We infer the minimal energy barrier to interlayer translation and observe soliton motion during in situ heating above 1,000 °C. The abundance of these structures across a variety of samples, as well as their unusual properties, suggests that they will have substantial effects on the electronic and mechanical properties of bilayer graphene. PMID:23798395

Electronic, Mechanical, and Dielectric Properties of Two-Dimensional Atomic Layers of Noble Metals

NASA Astrophysics Data System (ADS)

Kapoor, Pooja; Kumar, Jagdish; Kumar, Arun; Kumar, Ashok; Ahluwalia, P. K.

2017-01-01

We present density functional theory-based electronic, mechanical, and dielectric properties of monolayers and bilayers of noble metals (Au, Ag, Cu, and Pt) taken with graphene-like hexagonal structure. The Au, Ag, and Pt bilayers stabilize in AA-stacked configuration, while the Cu bilayer favors the AB stacking pattern. The quantum ballistic conductance of the noble-metal mono- and bilayers is remarkably increased compared with their bulk counterparts. Among the studied systems, the tensile strength is found to be highest for the Pt monolayer and bilayer. The noble metals in mono- and bilayer form show distinctly different electron energy loss spectra and reflectance spectra due to the quantum confinement effect on going from bulk to the monolayer limit. Such tunability of the electronic and dielectric properties of noble metals by reducing the degrees of freedom of electrons offers promise for their use in nanoelectronics and optoelectronics applications.

Bi-layer structure of counterstreaming energetic electron fluxes: a diagnostic tool of the acceleration mechanism in the Earth's magnetotail

NASA Astrophysics Data System (ADS)

Sarafopoulos, D. V.

2010-02-01

For the first time we identify a bi-layer structure of energetic electron fluxes in the Earth's magnetotail and establish (using datasets mainly obtained by the Geotail Energetic Particles and Ion Composition (EPIC/ICS) instrument) that it actually provides strong evidence for a purely spatial structure. Each bi-layer event is composed of two distinct layers with counterstreaming energetic electron fluxes, parallel and antiparallel to the local ambient magnetic field lines; in particular, the tailward directed fluxes always occur in a region adjacent to the lobes. Adopting the X-line as a standard reconnection model, we determine the occurrence of bi-layer events relatively to the neutral point, in the substorm frame; four (out of the shown seven) events are observed earthward and three tailward, a result implying that four events probably occurred with the substorm's local recovery phase. We discuss the bi-layer events in terms of the X-line model; they add more constraints for any candidate electron acceleration mechanism. It should be stressed that until this time, none proposed electron acceleration mechanism has discussed or predicted these layered structures with all their properties. Then we discuss the bi-layer events in terms of the much promising "akis model", as introduced by Sarafopoulos (2008). The akis magnetic field topology is embedded in a thinned plasma sheet and is potentially causing charge separation. We assume that as the Rc curvature radius of the magnetic field line tends to become equal to the ion gyroradius rg, then the ions become non-adiabatic. At the limit Rc=rg the demagnetization process is also under way and the frozen-in magnetic field condition is violated by strong wave turbulence; hence, the ion particles in this geometry are stochastically scattered. In addition, ion diffusion probably takes place across the magnetic field, since an intense pressure gradient is directed earthward; hence, ions are ejected tailward of akis. This way, in front of akis an "ion capsule region" is formed with net positive charge. In between them a distinct region with an electric field E⊥ orthogonal to the magnetic field is emerged; E⊥ in front of akis is directed earthward. The field-aligned and highly anisotropic energetic electron populations have probably resulted via spatially separated antiparallel and field-aligned electric fields being the very heart of the acceleration source. We assume that the ultimate cause for the field-aligned electric fields are the net positive capsule charge and the net negative charge trapped at the tip of akis; both charges will be eventually neutralized through field aligned currents, but they remain unshielded for sufficient time to produce the observed events.

Invited Article: Narrowband terahertz bandpass filters employing stacked bilayer metasurface antireflection structures

NASA Astrophysics Data System (ADS)

Chang, Chun-Chieh; Huang, Li; Nogan, John; Chen, Hou-Tong

2018-05-01

We experimentally demonstrate high-performance narrowband terahertz (THz) bandpass filters through cascading multiple bilayer metasurface antireflection structures. Each bilayer metasurface, consisting of a square array of silicon pillars with a self-aligned top gold resonator-array and a complementary bottom gold slot-array, enables near-zero reflection and simultaneously close-to-unity single-band transmission at designed operational frequencies in the THz spectral region. The THz bandpass filters based on stacked bilayer metasurfaces allow a fairly narrow, high-transmission passband, and a fast roll-off to an extremely clean background outside the passband, thereby providing superior bandpass performance. The demonstrated scheme of narrowband THz bandpass filtering is of great importance for a variety of applications where spectrally clean, high THz transmission over a narrow bandwidth is desired, such as THz spectroscopy and imaging, molecular detection and monitoring, security screening, and THz wireless communications.

Invited Article: Narrowband terahertz bandpass filters employing stacked bilayer metasurface antireflection structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Chun-Chieh; Huang, Li; Nogan, John

We experimentally demonstrate high-performance narrowband terahertz (THz) bandpass filters through cascading multiple bilayer metasurface antireflection structures. Each bilayer metasurface, consisting of a square array of silicon pillars with a self-aligned top gold resonator-array and a complementary bottom gold slot-array, enables near-zero reflection and simultaneously close-to-unity single-band transmission at designed operational frequencies in the THz spectral region. The THz bandpass filters based on stacked bilayer metasurfaces allow a fairly narrow, high-transmission passband, and a fast roll-off to an extremely clean background outside the passband, thereby providing superior bandpass performance. The demonstrated scheme of narrowband THz bandpass filtering is of great importancemore » for a variety of applications where spectrally clean, high THz transmission over a narrow bandwidth is desired, such as THz spectroscopy and imaging, molecular detection and monitoring, security screening, and THz wireless communications.« less

Invited Article: Narrowband terahertz bandpass filters employing stacked bilayer metasurface antireflection structures

DOE PAGES

Chang, Chun-Chieh; Huang, Li; Nogan, John; ...

2018-02-01

We experimentally demonstrate high-performance narrowband terahertz (THz) bandpass filters through cascading multiple bilayer metasurface antireflection structures. Each bilayer metasurface, consisting of a square array of silicon pillars with a self-aligned top gold resonator-array and a complementary bottom gold slot-array, enables near-zero reflection and simultaneously close-to-unity single-band transmission at designed operational frequencies in the THz spectral region. The THz bandpass filters based on stacked bilayer metasurfaces allow a fairly narrow, high-transmission passband, and a fast roll-off to an extremely clean background outside the passband, thereby providing superior bandpass performance. The demonstrated scheme of narrowband THz bandpass filtering is of great importancemore » for a variety of applications where spectrally clean, high THz transmission over a narrow bandwidth is desired, such as THz spectroscopy and imaging, molecular detection and monitoring, security screening, and THz wireless communications.« less

Ab initio studies of hydrogen adatoms on bilayer graphene

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Ukpong, A. M.; Chetty, N.

2012-05-01

We present a comparative density functional study of the adsorption of hydrogen on bilayer graphene. Six different exchange-correlation functionals are employed to explore the possible configurations of hydrogen adsorption at 50% coverage. Using the four variants of the nonlocal van der Waals density functional, we identify three distinct competing configurations that retain the coupled bilayer structure at 0 K. One of the configurations undergoes a spontaneous transformation from hexagonal to tetrahedral structure, under hydrogenation, with heat of formation ranging between -0.03 eV (vdW-DF) and -0.37 eV (vdW-DFC09x). This configuration has a finite band gap of around 3 eV, whereas all other competing configurations are either semimetallic or metallic. We also find two unique low-energy competing configurations of decoupled bilayer graphene, and therefore suggest the possibility of graphene exfoliation by hydrogen intercalation.

Magnetically Assisted Bilayer Composites for Soft Bending Actuators.

PubMed

Jang, Sung-Hwan; Na, Seon-Hong; Park, Yong-Lae

2017-06-12

This article presents a soft pneumatic bending actuator using a magnetically assisted bilayer composite composed of silicone polymer and ferromagnetic particles. Bilayer composites were fabricated by mixing ferromagnetic particles to a prepolymer state of silicone in a mold and asymmetrically distributed them by applying a strong non-uniform magnetic field to one side of the mold during the curing process. The biased magnetic field induces sedimentation of the ferromagnetic particles toward one side of the structure. The nonhomogeneous distribution of the particles induces bending of the structure when inflated, as a result of asymmetric stiffness of the composite. The bilayer composites were then characterized with a scanning electron microscopy and thermogravimetric analysis. The bending performance and the axial expansion of the actuator were discussed for manipulation applications in soft robotics and bioengineering. The magnetically assisted manufacturing process for the soft bending actuator is a promising technique for various applications in soft robotics.

Magnetically Assisted Bilayer Composites for Soft Bending Actuators

PubMed Central

Jang, Sung-Hwan; Na, Seon-Hong; Park, Yong-Lae

2017-01-01

This article presents a soft pneumatic bending actuator using a magnetically assisted bilayer composite composed of silicone polymer and ferromagnetic particles. Bilayer composites were fabricated by mixing ferromagnetic particles to a prepolymer state of silicone in a mold and asymmetrically distributed them by applying a strong non-uniform magnetic field to one side of the mold during the curing process. The biased magnetic field induces sedimentation of the ferromagnetic particles toward one side of the structure. The nonhomogeneous distribution of the particles induces bending of the structure when inflated, as a result of asymmetric stiffness of the composite. The bilayer composites were then characterized with a scanning electron microscopy and thermogravimetric analysis. The bending performance and the axial expansion of the actuator were discussed for manipulation applications in soft robotics and bioengineering. The magnetically assisted manufacturing process for the soft bending actuator is a promising technique for various applications in soft robotics. PMID:28773007

Mechanical properties of electrospun bilayer fibrous membranes as potential scaffolds for tissue engineering.

PubMed

Pu, Juan; Komvopoulos, Kyriakos

2014-06-01

Bilayer fibrous membranes of poly(l-lactic acid) (PLLA) were fabricated by electrospinning, using a parallel-disk mandrel configuration that resulted in the sequential deposition of a layer with fibers aligned across the two parallel disks and a layer with randomly oriented fibers, both layers deposited in a single process step. Membrane structure and fiber alignment were characterized by scanning electron microscopy and two-dimensional fast Fourier transform. Because of the intricacies of the generated electric field, bilayer membranes exhibited higher porosity than single-layer membranes consisting of randomly oriented fibers fabricated with a solid-drum collector. However, despite their higher porosity, bilayer membranes demonstrated generally higher elastic modulus, yield strength and toughness than single-layer membranes with random fibers. Bilayer membrane deformation at relatively high strain rates comprised multiple abrupt microfracture events characterized by discontinuous fiber breakage. Bilayer membrane elongation yielded excessive necking of the layer with random fibers and remarkable fiber stretching (on the order of 400%) in the layer with fibers aligned in the stress direction. In addition, fibers in both layers exhibited multiple localized necking, attributed to the nonuniform distribution of crystalline phases in the fibrillar structure. The high membrane porosity, good mechanical properties, and good biocompatibility and biodegradability of PLLA (demonstrated in previous studies) make the present bilayer membranes good scaffold candidates for a wide range of tissue engineering applications. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The Effect of Water and Confinement on Self-Assembly of Imidazolium Based Ionic Liquids at Mica Interfaces

PubMed Central

Cheng, H.-W.; Dienemann, J.-N.; Stock, P.; Merola, C.; Chen, Y.-J.; Valtiner, M.

2016-01-01

Tuning chemical structure and molecular layering of ionic liquids (IL) at solid interfaces offers leverage to tailor performance of ILs in applications such as super-capacitors, catalysis or lubrication. Recent experimental interpretations suggest that ILs containing cations with long hydrophobic tails form well-ordered bilayers at interfaces. Here we demonstrate that interfacial bilayer formation is not an intrinsic quality of hydrophobic ILs. In contrast, bilayer formation is triggered by boundary conditions including confinement, surface charging and humidity present in the IL. Therefore, we performed force versus distance profiles using atomic force microscopy and the surface forces apparatus. Our results support models of disperse low-density bilayer formation in confined situations, at high surface charging and/or in the presence of water. Conversely, interfacial structuring of long-chain ILs in dry environments and at low surface charging is disordered and dominated by bulk structuring. Our results demonstrate that boundary conditions such as charging, confinement and doping by impurities have decisive influence on structure formation of ILs at interfaces. As such, these results have important implications for understanding the behavior of solid/IL interfaces as they significantly extend previous interpretations. PMID:27452615

The Effect of Water and Confinement on Self-Assembly of Imidazolium Based Ionic Liquids at Mica Interfaces.

PubMed

Cheng, H-W; Dienemann, J-N; Stock, P; Merola, C; Chen, Y-J; Valtiner, M

2016-07-25

Tuning chemical structure and molecular layering of ionic liquids (IL) at solid interfaces offers leverage to tailor performance of ILs in applications such as super-capacitors, catalysis or lubrication. Recent experimental interpretations suggest that ILs containing cations with long hydrophobic tails form well-ordered bilayers at interfaces. Here we demonstrate that interfacial bilayer formation is not an intrinsic quality of hydrophobic ILs. In contrast, bilayer formation is triggered by boundary conditions including confinement, surface charging and humidity present in the IL. Therefore, we performed force versus distance profiles using atomic force microscopy and the surface forces apparatus. Our results support models of disperse low-density bilayer formation in confined situations, at high surface charging and/or in the presence of water. Conversely, interfacial structuring of long-chain ILs in dry environments and at low surface charging is disordered and dominated by bulk structuring. Our results demonstrate that boundary conditions such as charging, confinement and doping by impurities have decisive influence on structure formation of ILs at interfaces. As such, these results have important implications for understanding the behavior of solid/IL interfaces as they significantly extend previous interpretations.

Sum frequency generation (SFG) vibrational spectroscopy of planar phosphatidylethanolamine hybrid bilayer membranes under water.

PubMed

Kett, Peter J N; Casford, Michael T L; Davies, Paul B

2010-06-15

Sum frequency generation (SFG) spectroscopy has been used to study the structure of phosphatidylethanolamine hybrid bilayer membranes (HBMs) under water at ambient temperatures. The HBMs were formed using a modified Langmuir-Schaefer technique and consisted of a layer of dipalmitoyl phosphatidylethanolamine (DPPE) physisorbed onto an octadecanethiol (ODT) self-assembled monolayer (SAM) at a series of surface pressures from 1 to 40 mN m(-1). The DPPE and ODT were selectively deuterated so that the contributions to the SFG spectra from the two layers could be determined separately. SFG spectra in both the C-H and C-D stretching regions confirmed that a monolayer of DPPE had been adsorbed to the ODT SAM and that there were gauche defects within the alkyl chains of the phospholipid. On adsorption of a layer of DPPE, methylene modes from the ODT SAM were detected, indicating that the phospholipid had partially disordered the alkanethiol monolayer. SFG spectra recorded in air indicated that removal of water from the surface of the HBM resulted in disruption of the DPPE layer and the formation of phospholipid bilayers.

Fluorescence Spectroscopy in Thermodynamic and Kinetic Analysis of pH-Dependent Membrane Protein Insertion

PubMed Central

Ladokhin, Alexey S.

2016-01-01

Experimental determination of the free energy stabilizing the structure of membrane proteins in their native lipid environment is undermined by a lack of appropriate methods and suitable model systems. Here, we demonstrate how fluorescence correlation spectroscopy can be used to characterize thermodynamics of pH-triggered bilayer insertion of nonconstitutive membrane proteins (e.g., bacterial toxins, colicins). The experimental design is guided by the appropriate thermodynamic scheme which considers two independent processes: pH-dependent formation of a membrane-competent form and its insertion into the lipid bilayer. Measurements of a model protein annexin B12 under conditions of lipid saturation demonstrate that protonation leading to the formation of the membrane-competent state occurs near membrane interface. Lipid titration experiments demonstrate that the free energy of transfer to the intermediate interfacial state is especially favorable, while the free energy of final insertion is modulated by interplay of hydrophobic and electrostatic interactions on the bilayer interface. The general principles of kinetic measurements along the insertion pathway containing interfacial intermediate are discussed and practical examples emphasizing appropriate fitting and normalization procedures are presented. PMID:21609856

Hybrid lipid-based nanostructures

NASA Astrophysics Data System (ADS)

Dayani, Yasaman

Biological membranes serve several important roles, such as structural support of cells and organelles, regulation of ionic and molecular transport, barriers to non-mediated transport, contact between cells within tissues, and accommodation of membrane proteins. Membrane proteins and other vital biomolecules incorporated into the membrane need a lipid membrane to function. Due to importance of lipid bilayers and their vital function in governing many processes in the cell, the development of various models as artificial lipid membranes that can mimic cell membranes has become a subject of great interest. Using different models of artificial lipid membranes, such as liposomes, planar lipid bilayers and supported or tethered lipid bilayers, we are able to study many biophysical processes in biological membranes. The ability of different molecules to interact with and change the structure of lipid membranes can be also investigated in artificial lipid membranes. An important application of lipid bilayer-containing interfaces is characterization of novel membrane proteins for high throughput drug screening studies to investigate receptor-drug interactions and develop biosensor systems. Membrane proteins need a lipid bilayer environment to preserve their stability and functionality. Fabrication of materials that can interact with biomolecules like proteins necessitates the use of lipid bilayers as a mimic of cell membranes. The objective of this research is to develop novel hybrid lipid-based nanostructures mimicking biological membranes. Toward this aim, two hybrid biocompatible structures are introduced: lipid bilayer-coated multi-walled carbon nanotubes (MWCNTs) and hydrogel-anchored liposomes with double-stranded DNA anchors. These structures have potential applications in biosensing, drug targeting, drug delivery, and biophysical studies of cell membranes. In the first developed nanostructure, lipid molecules are covalently attached to the surfaces of MWCNTs, and then, using a sonication process, a uniform lipid bilayer that supports the incorporation of membrane proteins is formed. These bilayer-coated carbon nanotubes are highly dispersible and stable in aqueous solution, and they can be used in development of various biosensors and energy producing devices. In the other hybrid nanostructure, the lipid bilayer of a liposome is covalently anchored to a biocompatible poly(ethylene) glycol (PEG) hydrogel core using double-stranded DNA (dsDNA) linkers. Release studies shows that nano-size hydrogel-anchored liposomes are exceptionally stable, and they can be used as biomimetic model membranes that mimic the connectivity between the cytoskeleton and the plasma membrane. After lipid bilayer removal, dsDNA linkers can provide programmable nanogels decorated with oligonucleotides with potential sites for further molecular assembly. These stable nanostructures can be useful for oligonucleotide and drug delivery applications. The developed hydrogel-anchored liposomes are exploited for encapsulation and intracellular delivery of therapeutic peptide. Peptides with anti-cancer properties are successfully encapsulated in hydrogel core of pH-sensitive liposomes during rehydration process. Liposomes release their cargo at acidic pH. Confocal microscopy confirms the intracellular delivery of liposomes through an endocytotic pathway.

Membrane Fusion Proteins as Nanomachines

NASA Astrophysics Data System (ADS)

Tamm, Lukas

2009-03-01

Membrane fusion is key to fertilization, virus infection, and neurotransmission. Specific proteins work like nanomachines to stitch together fluid, yet highly ordered lipid bilayers. The energy gained from large exothermic conformational changes of these proteins is utilized to fuse lipid bilayers that do not fuse spontaneously. Structural studies using x-ray crystallography and NMR spectroscopy have yielded detailed information about architecture and inner workings of these molecular machines. The question now is: how is mechanical energy gained from such protein transformations harnessed to transform membrane topology? To answer this question, we have determined that a boomerang-shaped structure of the influenza fusion peptide is critical to generate a high-energy binding intermediate in the target membrane and to return the ``boomerang'' to its place of release near the viral membrane for completion of the fusion cycle. In presynaptic exocytosis, receptor and acceptor SNAREs are zippered to form a helical bundle that is arrested shortly before the membrane. Ca binding to interlocked synaptotagmin releases the fusion block. Structural NMR and single molecule fluorescence data are combined to arrive at and further refine this picture.

Detergent Optimized Membrane Protein Reconstitution in Liposomes for Solid State NMR

PubMed Central

2015-01-01

For small helical membrane proteins, their structures are highly sensitive to their environment, and solid state NMR is a structural technique that can characterize these membrane proteins in native-like lipid bilayers and proteoliposomes. To date, a systematic method by which to evaluate the effect of the solubilizing detergent on proteoliposome preparations for solid state NMR of membrane proteins has not been presented in the literature. A set of experiments are presented aimed at determining the conditions most amenable to dialysis mediated reconstitution sample preparation. A membrane protein from M. tuberculosis is used to illustrate the method. The results show that a detergent that stabilizes the most protein is not always ideal and sometimes cannot be removed by dialysis. By focusing on the lipid and protein binding properties of the detergent, proteoliposome preparations can be readily produced, which provide double the signal-to-noise ratios for both the oriented sample and magic angle spinning solid state NMR. The method will allow more membrane protein drug targets to be structurally characterized in lipid bilayer environments. PMID:24665863

Insight into the Putative Specific Interactions between Cholesterol, Sphingomyelin, and Palmitoyl-Oleoyl Phosphatidylcholine

PubMed Central

Aittoniemi, Jussi; Niemelä, Perttu S.; Hyvönen, Marja T.; Karttunen, Mikko; Vattulainen, Ilpo

2007-01-01

The effects of cholesterol (Chol) on phospholipid bilayers include ordering of the fatty acyl chains, condensing of the lipids in the bilayer plane, and promotion of the liquid-ordered phase. These effects depend on the type of phospholipids in the bilayer and are determined by the nature of the underlying molecular interactions. As for Chol, it has been shown to interact more favorably with sphingomyelin than with most phosphatidylcholines, which in given circumstances leads to formation of lateral domains. However, the exact origin and nature of Chol-phospholipid interactions have recently been subjects of speculation. We examine interactions between Chol, palmitoylsphingomyelin (PSM) and palmitoyl-oleoyl-phosphatidylcholine (POPC) in hydrated lipid bilayers by extensive atom-scale molecular dynamics simulations. We employ a tailored lipid configuration: Individual PSM and Chol monomers, as well as PSM-Chol dimers, are embedded in a POPC lipid bilayer in the liquid crystalline phase. Such a setup allows direct comparison of dimeric and monomeric PSMs and Chol, which ultimately shows how the small differences in PSM and POPC structure can lead to profoundly different interactions with Chol. Our analysis shows that direct hydrogen bonding between PSM and Chol does not provide an adequate explanation for their putative specific interaction. Rather, a combination of charge-pairing, hydrophobic, and van der Waals interactions leads to a lower tilt in PSM neighboring Chol than in Chol with only POPC neighbors. This implies improved Chol-induced ordering of PSM's chains over POPC's chains. These findings are discussed in the context of the hydrophobic mismatch concept suggested recently. PMID:17114220

Structure and hydration of membranes embedded with voltage-sensing domains.

PubMed

Krepkiy, Dmitriy; Mihailescu, Mihaela; Freites, J Alfredo; Schow, Eric V; Worcester, David L; Gawrisch, Klaus; Tobias, Douglas J; White, Stephen H; Swartz, Kenton J

2009-11-26

Despite the growing number of atomic-resolution membrane protein structures, direct structural information about proteins in their native membrane environment is scarce. This problem is particularly relevant in the case of the highly charged S1-S4 voltage-sensing domains responsible for nerve impulses, where interactions with the lipid bilayer are critical for the function of voltage-activated ion channels. Here we use neutron diffraction, solid-state nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics simulations to investigate the structure and hydration of bilayer membranes containing S1-S4 voltage-sensing domains. Our results show that voltage sensors adopt transmembrane orientations and cause a modest reshaping of the surrounding lipid bilayer, and that water molecules intimately interact with the protein within the membrane. These structural findings indicate that voltage sensors have evolved to interact with the lipid membrane while keeping energetic and structural perturbations to a minimum, and that water penetrates the membrane, to hydrate charged residues and shape the transmembrane electric field.

Structure and hydration of membranes embedded with voltage-sensing domains

PubMed Central

Krepkiy, Dmitriy; Mihailescu, Mihaela; Freites, J. Alfredo; Schow, Eric V.; Worcester, David L.; Gawrisch, Klaus; Tobias, Douglas; White, Stephen H.; Swartz, Kenton J.

2009-01-01

Despite the growing number of atomic-resolution membrane protein structures, direct structural information about proteins in their native membrane environment is scarce. This problem is particularly relevant in the case of the highly-charged S1–S4 voltage-sensing domains responsible for nerve impulses, where interactions with the lipid bilayer are critical for the function of voltage-activated potassium channels. Here we use neutron diffraction, solid-state nuclear magnetic resonance spectroscopy, and molecular dynamics simulations to investigate the structure and hydration of bilayer membranes containing S1–S4 voltage-sensing domains. Our results show that voltage sensors adopt transmembrane orientations, cause a modest reshaping of the surrounding lipid bilayer, and that water molecules intimately interact with the protein within the membrane. These structural findings reveal that voltage sensors have evolved to interact with the lipid membrane while keeping the energetic and structural perturbations to a minimum, and that water penetrates into the membrane to hydrate charged residues and shape the transmembrane electric field. PMID:19940918

High extinction ratio and low transmission loss thin-film terahertz polarizer with a tunable bilayer metal wire-grid structure.

PubMed

Huang, Zhe; Parrott, Edward P J; Park, Hongkyu; Chan, Hau Ping; Pickwell-MacPherson, Emma

2014-02-15

A thin-film terahertz polarizer is proposed and realized via a tunable bilayer metal wire-grid structure to achieve high extinction ratios and good transmission. The polarizer is fabricated on top of a thin silica layer by standard micro-fabrication techniques to eliminate the multireflection effects. The tunable alignment of the bilayer aluminum-wire grid structure enables tailoring of the extinction ratio and transmission characteristics. Using terahertz time-domain spectroscopy (THz-TDS), a fabricated polarizer is characterized, with extinction ratios greater than 50 dB and transmission losses below 1 dB reported in the 0.2-1.1 THz frequency range. These characteristics can be improved by further tuning the polarizer parameters such as the pitch, metal film thickness, and lateral displacement.

Closed-edged bilayer phosphorene nanoribbons producing from collapsing armchair phosphorene nanotubes.

PubMed

Liao, Xiangbiao; Xiao, Hang; Lu, Xiaobo; Chen, Youlong; Shi, Xiaoyang; Chen, Xi

2018-02-23

A new phosphorous allotrope, closed-edged bilayer phosphorene nanoribbon, is proposed via radially deforming armchair phosphorene nanotubes. Using molecular dynamics simulations, the transformation pathway from round PNTs falls into two types of collapsed structures: arc-like and sigmoidal bilayer nanoribbons, dependent on the number of phosphorene unit cells. The fabricated nanoribbions are energetically more stable than their parent nanotubes. It is also found via ab initio calculations that the band structure along tube axis substantially changes with the structural transformation. The direct-to-indirect transition of band gap is highlighted when collapsing into the arc-like nanoribbons but not the sigmoidal ones. Furthermore, the band gaps of these two types of nanoribbons show significant size-dependence of the nanoribbon width, indicative of wider tunability of their electrical properties.

Effect of sulphur vacancy and interlayer interaction on the electronic structure and spin splitting of bilayer MoS2.

PubMed

Dong, Yulan; Zeng, Bowen; Xiao, Jin; Zhang, Xiaojiao; Li, Dongde; Li, Mingjun; He, Jun; Long, Mengqiu

2018-02-27

Molybdenum disulfide (MoS 2 ) is one of the candidate materials for nanoelectronics and optoelectronics devices in the future. The electronic and magnetic properties of MoS 2 can be regulated by interlayer interaction and the vacancy effect. Nevertheless, the combined effect of these two factors on MoS 2 is not clearly understood. In this study, we have investigated the impact of a single S vacancy combined with interlayer interaction on the properties of bilayer MoS 2 . Our calculated results show that an S vacancy brings impurity states in the band structure of bilayer MoS 2 , and the energy level of the impurity states can be affected by the interlayer distance, which finally disappears in the bulk state when the layer distance is relatively small. Moreover, during the compression of bilayer MoS 2 , the bottom layer, where the S vacancy stays, gets an additional charge due to interlayer charge transfer, which first increases, and then decreases due to gradually forming the interlayer S-S covalent bond, as interlayer distance decreases. The change of the additional charge is consistent with the change of the total magnetic moment of the bottom layers, no magnetic moment has been found in the top layer. The distribution of magnetic moment mainly concentrates on the three Mo atoms around the S vacancy, for each of which the magnetic moment is very much related to the Mo-Mo length. Our conclusion is that the interlayer charge transfer and S vacancy co-determine the magnetic properties of this system, which may be a useful way to regulate the electronic and magnetic properties of MoS 2 for potential applications.

Effect of sulphur vacancy and interlayer interaction on the electronic structure and spin splitting of bilayer MoS2

NASA Astrophysics Data System (ADS)

Dong, Yulan; Zeng, Bowen; Xiao, Jin; Zhang, Xiaojiao; Li, Dongde; Li, Mingjun; He, Jun; Long, Mengqiu

2018-03-01

Molybdenum disulfide (MoS2) is one of the candidate materials for nanoelectronics and optoelectronics devices in the future. The electronic and magnetic properties of MoS2 can be regulated by interlayer interaction and the vacancy effect. Nevertheless, the combined effect of these two factors on MoS2 is not clearly understood. In this study, we have investigated the impact of a single S vacancy combined with interlayer interaction on the properties of bilayer MoS2. Our calculated results show that an S vacancy brings impurity states in the band structure of bilayer MoS2, and the energy level of the impurity states can be affected by the interlayer distance, which finally disappears in the bulk state when the layer distance is relatively small. Moreover, during the compression of bilayer MoS2, the bottom layer, where the S vacancy stays, gets an additional charge due to interlayer charge transfer, which first increases, and then decreases due to gradually forming the interlayer S-S covalent bond, as interlayer distance decreases. The change of the additional charge is consistent with the change of the total magnetic moment of the bottom layers, no magnetic moment has been found in the top layer. The distribution of magnetic moment mainly concentrates on the three Mo atoms around the S vacancy, for each of which the magnetic moment is very much related to the Mo-Mo length. Our conclusion is that the interlayer charge transfer and S vacancy co-determine the magnetic properties of this system, which may be a useful way to regulate the electronic and magnetic properties of MoS2 for potential applications.

Using a patterned grating structure to create lipid bilayer platforms insensitive to air bubbles.

PubMed

Han, Chung-Ta; Chao, Ling

2015-01-07

Supported lipid bilayers (SLBs) have been used for various biosensing applications. The bilayer structure enables embedded lipid membrane species to maintain their native orientation, and the two-dimensional fluidity is crucial for numerous biomolecular interactions to occur. The platform integrated with a microfluidic device for reagent transport and exchange has great potential to be applied with surface analytical tools. However, SLBs can easily be destroyed by air bubbles during assay reagent transport and exchange. Here, we created a patterned obstacle grating structured surface in a microfluidic channel to protect SLBs from being destroyed by air bubbles. Unlike all of the previous approaches using chemical modification or adding protection layers to strengthen lipid bilayers, the uniqueness of this approach is that it uses the patterned obstacles to physically trap water above the bilayers to prevent the air-water interface from directly coming into contact with and peeling the bilayers. We showed that our platform with certain grating geometry criteria can provide promising protection to SLBs from air bubbles. The required obstacle distance was found to decrease when we increased the air-bubble movement speed. In addition, the interaction assay results from streptavidin and biotinylated lipids in the confined SLBs suggested that receptors at the SLBs retained the interaction ability after air-bubble treatment. The results showed that the developed SLB platform can preserve both high membrane fluidity and high accessibility to the outside environment, which have never been simultaneously achieved before. Incorporating the built platforms with some surface analytical tools could open the bottleneck of building highly robust in vitro cell-membrane-related bioassays.

High Yield Chemical Vapor Deposition Growth of High Quality Large-Area AB Stacked Bilayer Graphene

PubMed Central

Liu, Lixin; Zhou, Hailong; Cheng, Rui; Yu, Woo Jong; Liu, Yuan; Chen, Yu; Shaw, Jonathan; Zhong, Xing; Huang, Yu; Duan, Xiangfeng

2012-01-01

Bernal stacked (AB stacked) bilayer graphene is of significant interest for functional electronic and photonic devices due to the feasibility to continuously tune its band gap with a vertical electrical field. Mechanical exfoliation can be used to produce AB stacked bilayer graphene flakes but typically with the sizes limited to a few micrometers. Chemical vapor deposition (CVD) has been recently explored for the synthesis of bilayer graphene but usually with limited coverage and a mixture of AB and randomly stacked structures. Herein we report a rational approach to produce large-area high quality AB stacked bilayer graphene. We show that the self-limiting effect of graphene growth on Cu foil can be broken by using a high H2/CH4 ratio in a low pressure CVD process to enable the continued growth of bilayer graphene. A high temperature and low pressure nucleation step is found to be critical for the formation of bilayer graphene nuclei with high AB stacking ratio. A rational design of a two-step CVD process is developed for the growth of bilayer graphene with high AB stacking ratio (up to 90 %) and high coverage (up to 99 %). The electrical transport studies demonstrated that devices made of the as-grown bilayer graphene exhibit typical characteristics of AB stacked bilayer graphene with the highest carrier mobility exceeding 4,000 cm2/V·s at room temperature, comparable to that of the exfoliated bilayer graphene. PMID:22906199

Edge effects on band gap energy in bilayer 2H-MoS{sub 2} under uniaxial strain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Liang; Wang, Jin; Dongare, Avinash M., E-mail: dongare@uconn.edu

2015-06-28

The potential of ultrathin MoS{sub 2} nanostructures for applications in electronic and optoelectronic devices requires a fundamental understanding in their electronic structure as a function of strain. Previous experimental and theoretical studies assume that an identical strain and/or stress state is always maintained in the top and bottom layers of a bilayer MoS{sub 2} film. In this study, a bilayer MoS{sub 2} supercell is constructed differently from the prototypical unit cell in order to investigate the layer-dependent electronic band gap energy in a bilayer MoS{sub 2} film under uniaxial mechanical deformations. The supercell contains an MoS{sub 2} bottom layer andmore » a relatively narrower top layer (nanoribbon with free edges) as a simplified model to simulate the as-grown bilayer MoS{sub 2} flakes with free edges observed experimentally. Our results show that the two layers have different band gap energies under a tensile uniaxial strain, although they remain mutually interacting by van der Waals interactions. The deviation in their band gap energies grows from 0 to 0.42 eV as the uniaxial strain increases from 0% to 6% under both uniaxial strain and stress conditions. The deviation, however, disappears if a compressive uniaxial strain is applied. These results demonstrate that tensile uniaxial strains applied to bilayer MoS{sub 2} films can result in distinct band gap energies in the bilayer structures. Such variations need to be accounted for when analyzing strain effects on electronic properties of bilayer or multilayered 2D materials using experimental methods or in continuum models.« less

Interaction of the Antimicrobial Peptide Aurein 1.2 and Charged Lipid Bilayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rai, Durgesh K.; Qian, Shuo

Aurein 1.2 is a potent antimicrobial peptide secreted by frog Litoria aurea. As a short membrane-active peptide with only 13 amino acids in sequence, it has been found to be residing on the surface of lipid bilayer and permeabilizing bacterial membranes at high concentration. However, the detail at the molecular level is largely unknown. Here in this study, we investigated the action of Aurein 1.2 in charged lipid bilayers composed of DMPC/DMPG. Oriented Circular Dichroism results showed that the peptide was on the surface of lipid bilayer regardless of the charged lipid ratio. Only at a very high peptide-to-lipid ratiomore » (~1/10), the peptide became perpendicular to the bilayer, however no pore was detected by neutron in-plane scattering. To further understand how it interacted with charged lipid bilayers, we employed Small Angle Neutron Scattering to probe lipid distribution across bilayer leaflets in lipid vesicles. The results showed that Aurein 1.2 interacted strongly with negatively charged DMPG, causing strong asymmetry in lipid bilayer. At high concentration, while the vesicles were intact, we found additional structure feature on the bilayer. Finally, our study provides a glimpse into how Aurein 1.2 disturbs anionic lipid-containing membranes without pore formation.« less

Interaction of the Antimicrobial Peptide Aurein 1.2 and Charged Lipid Bilayer

DOE PAGES

Rai, Durgesh K.; Qian, Shuo

2017-06-16

Aurein 1.2 is a potent antimicrobial peptide secreted by frog Litoria aurea. As a short membrane-active peptide with only 13 amino acids in sequence, it has been found to be residing on the surface of lipid bilayer and permeabilizing bacterial membranes at high concentration. However, the detail at the molecular level is largely unknown. Here in this study, we investigated the action of Aurein 1.2 in charged lipid bilayers composed of DMPC/DMPG. Oriented Circular Dichroism results showed that the peptide was on the surface of lipid bilayer regardless of the charged lipid ratio. Only at a very high peptide-to-lipid ratiomore » (~1/10), the peptide became perpendicular to the bilayer, however no pore was detected by neutron in-plane scattering. To further understand how it interacted with charged lipid bilayers, we employed Small Angle Neutron Scattering to probe lipid distribution across bilayer leaflets in lipid vesicles. The results showed that Aurein 1.2 interacted strongly with negatively charged DMPG, causing strong asymmetry in lipid bilayer. At high concentration, while the vesicles were intact, we found additional structure feature on the bilayer. Finally, our study provides a glimpse into how Aurein 1.2 disturbs anionic lipid-containing membranes without pore formation.« less

Relations for lipid bilayers. Connection of electron density profiles to other structural quantities.

PubMed Central

Nagle, J F; Wiener, M C

1989-01-01

Three relations are derived that connect low angle diffraction/scattering results obtained from lipid bilayers to other structural quantities of interest. The first relates the area along the surface of the bilayer, the measured specific volume, and the zeroth order structure factor, F(0). The second relates the size of the trough in the center of the electron density profile, the volume of the terminal methyl groups, and the volume of the methylene groups in the fatty acid chains. The third relates the size of the headgroup electron density peak, the volume of the headgroup, and the volumes of water and hydrocarbon in the headgroup region. These relations, which are easily modified for neutron diffraction, are useful for obtaining structural quantities from electron density profiles obtained by fitting model profiles to measured low angle x-ray intensities. PMID:2713444

Effect of shear stress on electromagnetic behaviors in superconductor-ferromagnetic bilayer structure

NASA Astrophysics Data System (ADS)

Yong, Huadong; Zhao, Meng; Jing, Ze; Zhou, Youhe

2014-09-01

In this paper, the electromagnetic response and shielding behaviour of superconductor-ferromagnetic bilayer structure are studied. The magnetomechanical coupling in ferromagnetic materials is also considered. Based on the linear piezomagnetic coupling model and anti-plane shear deformation, the current density and magnetic field in superconducting strip are obtained firstly. The effect of shear stress on the magnetization of strip is discussed. Then, we consider the magnetic cloak for superconductor-ferromagnetic bilayer structure. The magnetic permeability of ferromagnetic material is obtained for perfect cloaking in uniform magnetic field with magnetomechanical coupling in ferromagnet. The simulation results show that the electromagnetic response in superconductors will change by applying the stress only to the ferromagnetic material. In addition, the performance of invisibility of structure for non-uniform field will be affected by mechanical stress. It may provide a method to achieve tunability of superconducting properties with mechanical loadings.

Dye-sensitized solar cells consisting of dye-bilayer structure stained with two dyes for harvesting light of wide range of wavelength

NASA Astrophysics Data System (ADS)

Inakazu, Fumi; Noma, Yusuke; Ogomi, Yuhei; Hayase, Shuzi

2008-09-01

Dye-sensitized solar cells (DSCs) containing dye-bilayer structure of black dye and NK3705 (3-carboxymethyl-5-[3-(4-sulfobutyl)-2(3H)-bezothiazolylidene]-2-thioxo-4-thiazolidinone, sodium salt) in one TiO2 layer (2-TiO-BD-NK) are reported. The 2-TiO-BD-NK structure was fabricated by staining one TiO2 layer with these two dyes, step by step, under a pressurized CO2 condition. The dye-bilayer structure was observed by using a confocal laser scanning microscope. The short circuit current (Jsc) and the incident photon to current efficiency of the cell (DSC-2-TiO-BD-NK) was almost the sum of those of DSC stained with black dye only (DSC-1-TiO-BD) and DSC stained with NK3705 only (DSC-1-TiO-NK).

The Lγ Phase of Pulmonary Surfactant.

PubMed

Kumar, Kamlesh; Chavarha, Mariya; Loney, Ryan W; Weiss, Thomas M; Rananavare, Shankar B; Hall, Stephen B

2018-06-05

To determine how different components affect the structure of pulmonary surfactant, we measured X-ray scattering by samples derived from calf surfactant. The surfactant phospholipids demonstrated the essential characteristics of the L γ phase: a unit cell with a lattice constant appropriate for two bilayers, and crystalline chains detected by wide-angle X-ray scattering (WAXS). The electron density profile, obtained from scattering by oriented films at different relative humidities (70-97%), showed that the two bilayers, arranged as mirror images, each contain two distinct leaflets with different thicknesses and profiles. The detailed structures suggest one ordered leaflet that would contain crystalline chains and one disordered monolayer likely to contain the anionic compounds, which constitute ∼10% of the surfactant phospholipids. The spacing and temperature dependence detected by WAXS fit with an ordered leaflet composed of dipalmitoyl phosphatidylcholine. Physiological levels of cholesterol had no effect on this structure. Removing the anionic phospholipids prevented formation of the L γ phase. The cationic surfactant proteins inhibited L γ structures, but at levels unlikely related to charge. Because the L γ phase, if arranged properly, could produce a self-assembled ordered interfacial monolayer, the structure could have important functional consequences. Physiological levels of the proteins, however, inhibit formation of the L γ structures at high relative humidities, making their physiological significance uncertain.

Understanding the Interaction of Pluronics L61 and L64 with a DOPC Lipid Bilayer: An Atomistic Molecular Dynamics Study

DOE PAGES

Ileri Ercan, Nazar; Stroeve, Pieter; Tringe, Joseph W.; ...

2016-09-13

In this paper, we investigate the interactions of Pluronics L61 and L64 with a dioleylphosphatidylcholine (DOPC) lipid bilayer by atomistic molecular dynamics simulations using the all-atom OPLS force field. Our results show that the initial configuration of the polymer with respect to the bilayer determines its final conformation within the bilayer. When the polymer is initially placed at the lipid/water interface, we observe partial insertion of the polymer in a U-shaped conformation. On the other hand, when the polymer is centered at the bilayer, it stabilizes to a transmembrane state, which facilitates water transport across the bilayer. We show thatmore » membrane thickness decreases while its fluidity increases in the presence of Pluronics. When the polymer concentration inside the bilayer is high, pore formation is initiated with L64. Finally, our results show good agreement with existing experimental data and reveal that the hydrophilic/lipophilic balance of the polymer plays a critical role in the interaction mechanisms as well as in the dynamics of Pluronics with and within the bilayer.« less

Anomalous expansion of the copper-apical-oxygen distance in superconducting cuprate bilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hua; Yacoby, Yizhak; Butko, Vladimir Y.

2010-08-27

We have introduced an improved x-ray phase-retrieval method with unprecedented speed of convergence and precision, and used it to determine with sub-Angstrom resolution the complete atomic structure of epitaxial La{sub 2-x}Sr{sub x}CuO{sub 4} ultrathin films. We focus on superconducting heterostructures built from constituent materials that are not superconducting in bulk samples. Single-phase metallic or superconducting films are also studied for comparison. The results show that this phase-retrieval diffraction method enables accurate measurement of structural modifications in near-surface layers, which may be critically important for elucidation of surface-sensitive experiments. Specifically we find that, while the copper-apical-oxygen distance remains approximately constant inmore » single-phase films, it shows a dramatic increase from the metallic-insulating interface of the bilayer towards the surface by as much as 0.45 {angstrom}. The apical-oxygen displacement is known to have a profound effect on the superconducting transition temperature.« less

Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

PubMed Central

Cojal González, José D.; Iyoda, Masahiko; Rabe, Jürgen P.

2017-01-01

Fully conjugated macrocyclic oligothiophenes exhibit a combination of highly attractive structural, optical and electronic properties, and multifunctional molecular thin film architectures thereof are envisioned. However, control over the self-assembly of such systems becomes increasingly challenging, the more complex the target structures are. Here we show a robust self-assembly based on hierarchical non-covalent interactions. A self-assembled monolayer of hydrogen-bonded trimesic acid at the interface between an organic solution and graphite provides host-sites for the epitaxial ordering of Saturn-like complexes of fullerenes with oligothiophene macrocycles in mono- and bilayers. STM tomography verifies the formation of the templated layers. Molecular dynamics simulations corroborate the conformational stability and assign the adsorption sites of the adlayers. Scanning tunnelling spectroscopy determines their rectification characteristics. Current–voltage characteristics reveal the modification of the rectifying properties of the macrocycles by the formation of donor–acceptor complexes in a densely packed all-self-assembled supramolecular nanostructure. PMID:28281557

Templated bilayer self-assembly of fully conjugated π-expanded macrocyclic oligothiophenes complexed with fullerenes

NASA Astrophysics Data System (ADS)

Cojal González, José D.; Iyoda, Masahiko; Rabe, Jürgen P.

2017-03-01

Fully conjugated macrocyclic oligothiophenes exhibit a combination of highly attractive structural, optical and electronic properties, and multifunctional molecular thin film architectures thereof are envisioned. However, control over the self-assembly of such systems becomes increasingly challenging, the more complex the target structures are. Here we show a robust self-assembly based on hierarchical non-covalent interactions. A self-assembled monolayer of hydrogen-bonded trimesic acid at the interface between an organic solution and graphite provides host-sites for the epitaxial ordering of Saturn-like complexes of fullerenes with oligothiophene macrocycles in mono- and bilayers. STM tomography verifies the formation of the templated layers. Molecular dynamics simulations corroborate the conformational stability and assign the adsorption sites of the adlayers. Scanning tunnelling spectroscopy determines their rectification characteristics. Current-voltage characteristics reveal the modification of the rectifying properties of the macrocycles by the formation of donor-acceptor complexes in a densely packed all-self-assembled supramolecular nanostructure.

Structure of single-supported DMPC lipid bilayer membranes as a function of hydration level studied by neutron reflectivity and Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Miskowiec, A.; Schnase, P.; Bai, M.; Taub, H.; Hansen, F. Y.; Dubey, M.; Singh, S.; Majewski, J.

2012-02-01

We have recently been investigating the diffusion of water on single-supported DMPC lipid bilayer membranes at different levels of hydration, using high-resolution quasielastic neutron scattering (QNS). To aid in the interpretation of these QNS studies, we have conducted neutron reflectivity (NR) measurements on SPEAR at LANSCE to characterize the structure of similarly prepared samples. Protonated DMPC membranes were deposited onto SiO2-coated Si(100) substrates and characterized by Atomic Force Microscopy (AFM) at different levels of hydration. We find reasonable agreement between the membrane thickness determined by NR and AFM at room temperature. We also find consistency between the scattering length density (SLD) profile in the vicinity of the upper leaflet of the supported DMPC membrane and that found in a molecular dynamics simulation of a freestanding membrane at 303 K. However, the fit to the reflectivity curve can be improved by modifying the SLD profile near the leaflet closest to the SiO2 surface.

Moiré edge states in twisted graphene nanoribbons

NASA Astrophysics Data System (ADS)

Fleischmann, M.; Gupta, R.; Weckbecker, D.; Landgraf, W.; Pankratov, O.; Meded, V.; Shallcross, S.

2018-05-01

The edge physics of graphene based systems is well known to be highly sensitive to the atomic structure at the boundary, with localized zero mode edge states found only on the zigzag-type termination of the lattice. Here we demonstrate that the graphene twist bilayer supports an additional class of edge states, that (i) are found for all edge geometries and thus are robust against edge roughness, (ii) occur at energies coinciding with twist induced Van Hove singularities in the bulk and (iii) possess an electron density strongly modulated by the moiré lattice. Interestingly, these "moiré edge states" exist only for certain lattice commensurations and thus the edge physics of the twist bilayer is, in dramatic contrast to that of the bulk, not uniquely determined by the twist angle.

Magnetoelectric effect in bilayer graphene controlled by valley-isospin density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zülicke, U.; Winkler, R.

2014-09-01

We show that bilayer graphene (BLG) exhibits magnetoelectric (ME) effects that are formally similar to those commonly seen in band insulators with broken inversion and time-reversal symmetries. Three unusual features characterize the ME responses exhibited by BLG: (i) unlike most other ME media, BLG is a conductor, (ii) BLG has a nonquantized ME coupling even though its electronic structure does not break parity and time-reversal symmetry, and (iii) the magnitude of the ME coupling in BLG is determined by the valley-isospin density, which can be manipulated experimentally. This last property also enables a purely electric measurement of valley-isospin densities. Whilemore » our theoretical arguments use BLG as an example, they are generally valid for any material with similar symmetries« less

Explanation of ν=−12 fractional quantum Hall state in bilayer graphene

PubMed Central

Jacak, L.

2016-01-01

The commensurability condition is applied to determine the hierarchy of fractional filling of Landau levels for fractional quantum Hall effect (FQHE) in monolayer and bilayer graphene. Good agreement with experimental data is achieved. The presence of even-denominator filling fractions in the hierarchy of the FQHE in bilayer graphene is explained, including the state at ν=−12. PMID:27118883

Magnetotransport of High Mobility Holes in Monolayer and Bilayer WSe2

NASA Astrophysics Data System (ADS)

Tutuc, Emanuel

Transition metal dichalcogenides have attracted significant interest because of their two-dimensional crystal structure, large band-gap, and strong spin-orbit interaction which leads to spin-valley locking. Recent advances in sample fabrication have allowed the experimental study of low temperature magneto-transport of high mobility holes in WSe2. We review here the main results of these studies which reveal clear quantum Hall states in mono- and bilayer WSe2. The data allows the extraction of an effective hole mass of m* = 0.45me (me is the bare electron mass) in both mono and bilayer WSe2. A systematic study of the carrier distribution in bilayer WSe2 determined from a Fourier analysis of the Shubnikov-de Haas oscillations indicates that the two layers are weakly coupled. The individual layer density dependence on gate bias shows negative compressibility, a signature of strong electron-electron interaction in these materials associated with the large effective mass. We discuss the interplay between cyclotron and Zeeman splitting using the dependence of the quantum Hall state sequence on carrier density, and the angle between the magnetic field and the WSe2 plane. Work done in collaboration with B. Fallahazad, H. C. P. Movva, K. Kim, S. K. Banerjee, T. Taniguchi, and K. Watanabe. This work supported by the Nanoelectronics Research Initiative SWAN center, Intel Corp., and National Science Foundation.

Evaluation of Maltose-Induced Chemical Degradation at the Interface of Bilayer Tablets.

PubMed

Matsuzaki, Naoya; Yamamoto, Yousuke; Murayama, Daisuke; Katakawa, Yoshifumi; Mimura, Hisashi; Kimura, Shin-Ichiro; Iwao, Yasunori; Itai, Shigeru

2017-01-01

Fixed dose combination tablets consisting of mirabegron (MB) and solifenacin succinate (SS) were developed and formulated into bilayer tablets in the current study. The results of a chemical stability study showed that the original formulation for the tablets led to a significant increase of unknown degradants in the SS layer. Two compatibility studies were conducted to simulate the interface between the MB and SS layers, and the results revealed that the degradants only formed in the presence of both active pharmaceutical ingredients (APIs), and that the presence of maltose in the SS layer was critical to inducing degradation. High resolution mass spectroscopy coupled with high performance liquid chromatography was used to determine the chemical structures of the degradants, which were identified to MB derivatives bearing one or two sugar units. These findings therefore suggested that the degradation of the API could be attributed to the addition of sugar units from maltose to MB under the acidic conditions caused by SS. With this in mind, we developed a new formulation by replacing maltose with hydroxypropyl cellulose as a polymer-type binder. The results showed that this formulation suppressed the formation of the degradants. The results of this study have shown that chemical degradation can occur at the interface of bilayer tablets and that an alternative strategy is available to formulate more stable MB/SS bilayer tablets.

Permeability of acetic acid across gel and liquid-crystalline lipid bilayers conforms to free-surface-area theory.

PubMed Central

Xiang, T X; Anderson, B D

1997-01-01

Solubility-diffusion theory, which treats the lipid bilayer membrane as a bulk lipid solvent into which permeants must partition and diffuse across, fails to account for the effects of lipid bilayer chain order on the permeability coefficient of any given permeant. This study addresses the scaling factor that must be applied to predictions from solubility-diffusion theory to correct for chain ordering. The effects of bilayer chemical composition, temperature, and phase structure on the permeability coefficient (Pm) of acetic acid were investigated in large unilamellar vesicles by a combined method of NMR line broadening and dynamic light scattering. Permeability values were obtained in distearoylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, and dilauroylphosphatidylcholine bilayers, and their mixtures with cholesterol, at various temperatures both above and below the gel-->liquid-crystalline phase transition temperatures (Tm). A new scaling factor, the permeability decrement f, is introduced to account for the decrease in permeability coefficient from that predicted by solubility-diffusion theory owing to chain ordering in lipid bilayers. Values of f were obtained by division of the observed Pm by the permeability coefficient predicted from a bulk solubility-diffusion model. In liquid-crystalline phases, a strong correlation (r = 0.94) between f and the normalized surface density sigma was obtained: in f = 5.3 - 10.6 sigma. Activation energies (Ea) for the permeability of acetic acid decreased with decreasing phospholipid chain length and correlated with the sensitivity of chain ordering to temperature, [symbol: see text] sigma/[symbol: see text](1/T), as chain length was varied. Pm values decreased abruptly at temperatures below the main phase transition temperatures in pure dipalmitoylphosphatidylcholine and dimyristoylphosphatidylcholine bilayers (30-60-fold) and below the pretransition in dipalmitoylphosphatidylcholine bilayers (8-fold), and the linear relationship between in f and sigma established for liquid-crystalline bilayers was no longer followed. However, in both gel and liquid-crystalline phases in f was found to exhibit an inverse correlation with free surface area (in f = -0.31 - 29.1/af, where af is the average free area (in square angstroms) per lipid molecule). Thus, the lipid bilayer permeability of acetic acid can be predicted from the relevant chain-packing properties in the bilayer (free surface area), regardless of whether chain ordering is varied by changes in temperature, lipid chain length, cholesterol concentration, or bilayer phase structure, provided that temperature effects on permeant dehydration and diffusion and the chain-length effects on bilayer barrier thickness are properly taken into account. PMID:8994607

Electric field-triggered metal-insulator transition resistive switching of bilayered multiphasic VOx

NASA Astrophysics Data System (ADS)

Won, Seokjae; Lee, Sang Yeon; Hwang, Jungyeon; Park, Jucheol; Seo, Hyungtak

2018-01-01

Electric field-triggered Mott transition of VO2 for next-generation memory devices with sharp and fast resistance-switching response is considered to be ideal but the formation of single-phase VO2 by common deposition techniques is very challenging. Here, VOx films with a VO2-dominant phase for a Mott transition-based metal-insulator transition (MIT) switching device were successfully fabricated by the combined process of RF magnetron sputtering of V metal and subsequent O2 annealing to form. By performing various material characterizations, including scanning transmission electron microscopy-electron energy loss spectroscopy, the film is determined to have a bilayer structure consisting of a VO2-rich bottom layer acting as the Mott transition switching layer and a V2O5/V2O3 mixed top layer acting as a control layer that suppresses any stray leakage current and improves cyclic performance. This bilayer structure enables excellent electric field-triggered Mott transition-based resistive switching of Pt-VOx-Pt metal-insulator-metal devices with a set/reset current ratio reaching 200, set/reset voltage of less than 2.5 V, and very stable DC cyclic switching upto 120 cycles with a great set/reset current and voltage distribution less than 5% of standard deviation at room temperature, which are specifications applicable for neuromorphic or memory device applications. [Figure not available: see fulltext.

Intrinsic Curvature-Mediated Transbilayer Coupling in Asymmetric Lipid Vesicles

DOE PAGES

Eicher, Barbara; Marquardt, Drew; Heberle, Frederick A.; ...

2018-01-09

We measured the effect of intrinsic lipid curvature, J 0, on structural properties of asymmetric vesicles made of palmitoyl-oleoyl-phosphatidylethanolamine (POPE; J 0 < 0) and palmitoyl-oleoyl-phosphatidylcholine (POPC; J 0 ~ 0). Electron microscopy and dynamic light scattering were used to determine vesicle size and morphology, and x-ray and neutron scattering, combined with calorimetric experiments and solution NMR, yielded insights into leaflet-specific lipid packing and melting processes. Below the lipid melting temperature we observed strong interleaflet coupling in asymmetric vesicles with POPE inner bilayer leaflets and outer leaflets enriched in POPC. This lipid arrangement manifested itself by lipids melting cooperatively inmore » both leaflets, and a rearrangement of lipid packing in both monolayers. On the other hand, no coupling was observed in vesicles with POPC inner bilayer leaflets and outer leaflets enriched in POPE. In this case, the leaflets melted independently and did not affect each other’s acyl chain packing. Furthermore, we found no evidence for transbilayer structural coupling above the melting temperature of either sample preparation. Our results are consistent with the energetically preferred location of POPE residing in the inner leaflet, where it also resides in natural membranes, most likely causing the coupling of both leaflets. The loss of this coupling in the fluid bilayers is most likely the result of entropic contributions.« less

Molecular dynamics simulation of unsaturated lipid bilayers at low hydration: parameterization and comparison with diffraction studies.

PubMed Central

Feller, S E; Yin, D; Pastor, R W; MacKerell, A D

1997-01-01

A potential energy function for unsaturated hydrocarbons is proposed and is shown to agree well with experiment, using molecular dynamics simulations of a water/octene interface and a dioleoyl phosphatidylcholine (DOPC) bilayer. The simulation results verify most of the assumptions used in interpreting the DOPC experiments, but suggest a few that should be reconsidered. Comparisons with recent results of a simulation of a dipalmitoyl phosphatidylcholine (DPPC) lipid bilayer show that disorder is comparable, even though the temperature, hydration level, and surface area/lipid for DOPC are lower. These observations highlight the dramatic effects of unsaturation on bilayer structure. Images FIGURE 3 PMID:9370424

Neutron Scattering Studies of the Interplay of Amyloid β Peptide(1–40) and An Anionic Lipid 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol

DOE PAGES

Rai, Durgesh K.; Sharma, Veerendra K.; Anunciado, Divina; ...

2016-08-09

The interaction between lipid bilayers and Amyloid β peptide (Aβ) plays a critical role in proliferation of Alzheimer’s disease (AD). AD is expected to affect one in every 85 humans by 2050, and therefore, deciphering the interplay of Aβ and lipid bilayers at the molecular level is of profound importance. In this work, we applied an array of neutron scattering methods to study the structure and dynamics of Aβ(1–40) interacting 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol (DMPG) bilayers. In the structural investigations of lipid bilayer’s response to Aβ binding, Small Angle Neutron Scattering and Neutron Membrane Diffraction revealed that the Aβ anchors firmly to themore » highly charged DMPG bilayers in the interfacial region between water and hydrocarbon chain, and it doesn’t penetrate deeply into the bilayer. This association mode is substantiated by the dynamics studies with high resolution Quasi-Elastic Neutron Scattering experiments, showing that the addition of Aβ mainly affects the slower lateral motion of lipid molecules, especially in the fluid phase, but not the faster internal motion. The results revealed that Aβ associates with the highly charged membrane in surface with limited impact on the structure, but the altered membrane dynamics could have more influence on other membrane processes.« less

Mixing and Matching Detergents for Membrane Protein NMR Structure Determination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Columbus, Linda; Lipfert, Jan; Jambunathan, Kalyani

2009-10-21

One major obstacle to membrane protein structure determination is the selection of a detergent micelle that mimics the native lipid bilayer. Currently, detergents are selected by exhaustive screening because the effects of protein-detergent interactions on protein structure are poorly understood. In this study, the structure and dynamics of an integral membrane protein in different detergents is investigated by nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopy and small-angle X-ray scattering (SAXS). The results suggest that matching of the micelle dimensions to the protein's hydrophobic surface avoids exchange processes that reduce the completeness of the NMR observations. Based onmore » these dimensions, several mixed micelles were designed that improved the completeness of NMR observations. These findings provide a basis for the rational design of mixed micelles that may advance membrane protein structure determination by NMR.« less

Revealing the correlation between real-space structure and chiral magnetic order at the atomic scale

NASA Astrophysics Data System (ADS)

Hauptmann, Nadine; Dupé, Melanie; Hung, Tzu-Chao; Lemmens, Alexander K.; Wegner, Daniel; Dupé, Bertrand; Khajetoorians, Alexander A.

2018-03-01

We image simultaneously the geometric, the electronic, and the magnetic structures of a buckled iron bilayer film that exhibits chiral magnetic order. We achieve this by combining spin-polarized scanning tunneling microscopy and magnetic exchange force microscopy (SPEX) to independently characterize the geometric as well as the electronic and magnetic structures of nonflat surfaces. This new SPEX imaging technique reveals the geometric height corrugation of the reconstruction lines resulting from strong strain relaxation in the bilayer, enabling the decomposition of the real-space from the electronic structure at the atomic level and the correlation with the resultant spin-spiral ground state. By additionally utilizing adatom manipulation, we reveal the chiral magnetic ground state of portions of the unit cell that were not previously imaged with spin-polarized scanning tunneling microscopy alone. Using density functional theory, we investigate the structural and electronic properties of the reconstructed bilayer and identify the favorable stoichiometry regime in agreement with our experimental result.

Structure stability of lytic peptides during their interactions with lipid bilayers.

PubMed

Chen, H M; Lee, C H

2001-10-01

In this work, molecular dynamics simulations were used to examine the consequences of a variety of analogs of cecropin A on lipid bilayers. Analog sequences were constructed by replacing either the N- or C-terminal helix with the other helix in native or reverse sequence order, by making palindromic peptides based on both the N- and C-terminal helices, and by deleting the hinge region. The structure of the peptides was monitored throughout the simulation. The hinge region appeared not to assist in maintaining helical structure but help in motion flexibility. In general, the N-terminal helix of peptides was less stable than the C-terminal one during the interaction with anionic lipid bilayers. Sequences with hydrophobic helices tended to regain helical structure after an initial loss while sequences with amphipathic helices were less able to do this. The results suggests that hydrophobic design peptides have a high structural stability in an anionic membrane and are the candidates for experimental investigation.

Investigating Hydrophilic Pores in Model Lipid Bilayers using Molecular Simulations: Correlating Bilayer Properties with Pore Formation Thermodynamics

PubMed Central

Hu, Yuan; Sinha, Sudipta Kumar

2015-01-01

Cell-penetrating and antimicrobial peptides show remarkable ability to translocate across physiological membranes. Along with factors such as electric potential induced-perturbations of membrane structure and surface tension effects, experiments invoke pore-like membrane configurations during the solute transfer process into vesicles and cells. The initiation and formation of pores are associated with a non-trivial free energy cost, thus necessitating consideration of the factors associated with pore formation and attendant free energetics. Due to experimental and modeling challenges related to the long timescales of the translocation process, we use umbrella-sampling molecular dynamics simulations with a lipid-density based order parameter to investigate membrane pore-formation free energy employing Martini coarse-grained models. We investigate structure and thermodynamic features of the pore in 18 lipids spanning a range of head-groups, charge states, acyl chain lengths and saturation. We probe the dependence of pore-formation barriers on area per lipid, lipid bilayer thickness, membrane bending rigidities in three different lipid classes. The pore formation free energy in pure bilayers and peptide translocating scenarios are significantly coupled with bilayer thickness. Thicker bilayers require more reversible work to create pores. Pore formation free energy is higher in peptide-lipid systems relative to the peptide-free lipid systems due to penalties to maintain solvation of charged hydrophilic solutes within the membrane environment. PMID:25614183

Investigating Hydrophilic Pores in Model Lipid Bilayers Using Molecular Simulations: Correlating Bilayer Properties with Pore-Formation Thermodynamics.

PubMed

Hu, Yuan; Sinha, Sudipta Kumar; Patel, Sandeep

2015-06-23

Cell-penetrating and antimicrobial peptides show a remarkable ability to translocate across physiological membranes. Along with factors such as electric-potential-induced perturbations of membrane structure and surface tension effects, experiments invoke porelike membrane configurations during the solute transfer process into vesicles and cells. The initiation and formation of pores are associated with a nontrivial free-energy cost, thus necessitating a consideration of the factors associated with pore formation and the attendant free energies. Because of experimental and modeling challenges related to the long time scales of the translocation process, we use umbrella sampling molecular dynamics simulations with a lipid-density-based order parameter to investigate membrane-pore-formation free energy employing Martini coarse-grained models. We investigate structure and thermodynamic features of the pore in 18 lipids spanning a range of headgroups, charge states, acyl chain lengths, and saturation. We probe the dependence of pore-formation barriers on the area per lipid, lipid bilayer thickness, and membrane bending rigidities in three different lipid classes. The pore-formation free energy in pure bilayers and peptide translocating scenarios are significantly coupled with bilayer thickness. Thicker bilayers require more reversible work to create pores. The pore-formation free energy is higher in peptide-lipid systems than in peptide-free lipid systems due to penalties to maintain the solvation of charged hydrophilic solutes within the membrane environment.

Importance of Residue 13 and the C-Terminus for the Structure and Activity of the Antimicrobial Peptide Aurein 2.2

PubMed Central

Cheng, John T.J.; Hale, John D.; Kindrachuk, Jason; Jessen, Havard; Elliott, Melissa; Hancock, Robert E.W.; Straus, Suzana K.

2010-01-01

Previous studies on aurein 2.2 and 2.3 in DMPC/DMPG and POPC/POPG membranes have shown that bilayer thickness and phosphatidylglycerol content have a significant impact on the interaction of these peptides with membrane bilayers. Further examination with the DiSC35 assay has indicated that aurein 2.2 induces greater membrane leakage than aurein 2.3 in Staphylococcus aureus C622. The only difference between these peptides is a Leu to Ile mutation at residue 13. To better understand the importance of this residue, the structure and activity of the L13A, L13F, and L13V mutants were investigated. In addition, we investigated a number of peptides with truncations at the C-terminus to determine whether the C-terminus, which contains residue 13, is crucial for antimicrobial activity. Solution circular dichroism results demonstrated that the L13F mutation and the truncation of the C-terminus by six residues resulted in decreased helical content, whereas the L13A or L13V mutation and the truncation of the C-terminus by three residues showed little to no effect on the structure. Oriented circular dichroism results demonstrated that only an extensive C-terminal truncation reduced the ability of the peptide to insert into lipid bilayers. 31P NMR spectroscopy showed that all peptides disorder the headgroups. The implications of these results in terms of antimicrobial activity and the ability of these peptides to induce leakage in S. aureus are discussed. The results suggest that the presence of the 13th residue in aurein 2.2 is important for structure and activity, but the exact nature of residue 13 is less important as long as it is a hydrophobic residue. PMID:21044590

Calcein release behavior from liposomal bilayer; influence of physicochemical/mechanical/structural properties of lipids.

PubMed

Maherani, Behnoush; Arab-Tehrany, Elmira; Kheirolomoom, Azadeh; Geny, David; Linder, Michel

2013-11-01

The design of the drug delivery depends upon different parameters. One of the most noticeable factors in design of the drug delivery is drug-release profile which determines the site of action, the concentration of the drug at the time of administration, the period of time that the drug must remain at a therapeutic concentration. To get a better understanding of drug release, large unilamellar liposomes containing calcein were prepared using 1,2-dioleoyl-sn-glycero-3-phosphocholine, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine and 1,2-palmitoyl-sn-glycero-3-phosphocholine, and a mixture of them; calcein was chosen as a model of hydrophilic drug. The calcein permeability across liposomal membrane (with different compositions) was evaluated on the basis of the first-order kinetic by spectrofluorometer. Also, the effects of liposome composition/fluidity as well as the incubation temperature/pH were investigated. Furthermore, we simulated the digestion condition in the gastrointestinal tract in humans, to mimic human gastro-duodenal digestion to monitor calcein release during the course of the digestion process. In vitro digestion model ''pH stat'' was used to systematically examine the influence of pH/enzyme on phospholipid liposomes digestion under simulated gastro-duodenal digestion. The results revealed that calcein permeates across liposomal membrane without membrane disruption. The release rate of calcein from the liposomes depends on the number and fluidity of bilayers and its mechanical/physical properties such as permeability, bending elasticity. Chemo-structural properties of drugs like as partition coefficient (Log P), H-bonding, polar surface area (PSA) are also determinative parameter in release behavior. Finally, stimulated emission depletion (STED) microscopy was used to study calcein translocation through liposomal bilayers. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Li; Thompson, Gregory, E-mail: gthompson@eng.ua.edu

A series of 40–2 nm bilayer spacing Ti/Fe multilayers were sputter-deposited. As the length scale of individual Ti layers equaled to 2 nm, Ti phase transforms from a hexagonal close packed (hcp)-to-body centered cubic (bcc) crystal structures for equal layer thicknesses in Ti/Fe multilayers. Further equal reductions in bilayer spacing to less than 1 nm resulted in an additional transformation from a crystalline to amorphous structure. Atom probe tomography reveals significant intermixing between layers which contributes to the observed phase transformations. Real-time, intrinsic growth stress measurements were also performed to relate the adatom mobility to these phase transformations. For the hcp Ti/bcc Femore » multilayers of equivalent volume fractions, the multilayers undergo an overall tensile stress state to a compressive stress state with decreasing bilayer thickness for the multilayers. When the above phase transformations occurred, a modest reduction in the overall compressive stress of the multilayer was noted. Depending on the Fe thickness, the Ti growth was observed to be a tensile to compressive growth change to a purely compressive growth for thinner bilayer spacing. Fe retained a tensile growth stress regardless of the bilayer spacing studied.« less

Aggregation of Aß(25-35) on DOPC and DOPC/DHA bilayers: an atomic force microscopy study.

PubMed

Sublimi Saponetti, Matilde; Grimaldi, Manuela; Scrima, Mario; Albonetti, Cristiano; Nori, Stefania Lucia; Cucolo, Annamaria; Bobba, Fabrizio; D'Ursi, Anna Maria

2014-01-01

β amyloid peptide plays an important role in both the manifestation and progression of Alzheimer disease. It has a tendency to aggregate, forming low-molecular weight soluble oligomers, higher-molecular weight protofibrillar oligomers and insoluble fibrils. The relative importance of these single oligomeric-polymeric species, in relation to the morbidity of the disease, is currently being debated. Here we present an Atomic Force Microscopy (AFM) study of Aβ(25-35) aggregation on hydrophobic dioleoylphosphatidylcholine (DOPC) and DOPC/docosahexaenoic 22∶6 acid (DHA) lipid bilayers. Aβ(25-35) is the smallest fragment retaining the biological activity of the full-length peptide, whereas DOPC and DOPC/DHA lipid bilayers were selected as models of cell-membrane environments characterized by different fluidity. Our results provide evidence that in hydrophobic DOPC and DOPC/DHA lipid bilayers, Aβ(25-35) forms layered aggregates composed of mainly annular structures. The mutual interaction between annular structures and lipid surfaces end-results into a membrane solubilization. The presence of DHA as a membrane-fluidizing agent is essential to protect the membrane from damage caused by interactions with peptide aggregates; to reduces the bilayer defects where the delipidation process starts.

Tuning the energy gap of bilayer α-graphyne by applying strain and electric field

NASA Astrophysics Data System (ADS)

Yang, Hang; Wu, Wen-Zhi; Jin, Yu; Wan-Lin, Guo

2016-02-01

Our density functional theory calculations show that the energy gap of bilayer α-graphyne can be modulated by a vertically applied electric field and interlayer strain. Like bilayer graphene, the bilayer α-graphyne has electronic properties that are hardly changed under purely mechanical strain, while an external electric field can open the gap up to 120 meV. It is of special interest that compressive strain can further enlarge the field induced gap up to 160 meV, while tensile strain reduces the gap. We attribute the gap variation to the novel interlayer charge redistribution between bilayer α-graphynes. These findings shed light on the modulation of Dirac cone structures and potential applications of graphyne in mechanical-electric devices. Project supported by the National Key Basic Research Program of China (Grant Nos. 2013CB932604 and 2012CB933403), the National Natural Science Foundation of China (Grant Nos. 51472117 and 51535005), the Research Fund of State Key Laboratory of Mechanics and Control of Mechanical Structures, China (Grant No. 0414K01), the Nanjing University of Aeronautics and Astronautics (NUAA) Fundamental Research Funds, China (Grant No. NP2015203), and the Priority Academic Program Development of Jiangsu Higher Education Institutions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sadovnikov, A. V., E-mail: sadovnikovav@gmail.com; Nikitov, S. A.; Kotel'nikov Institute of Radioengineering and Electronics, Russian Academy of Sciences, Moscow 125009

Using the space-resolved Brillouin light scattering spectroscopy we study the transformation of dynamic magnetization patterns in a bilayer multiferroic structure. We show that in the comparison with a single yttrium iron garnet (YIG) film magnetization distribution is transformed in the bilayer structure due to the coupling of waves propagating both in an YIG film (magnetic layer) and in a barium strontium titanate slab (ferroelectric layer). We present a simple electrodynamic model using the numerical finite element method to show the transformation of eigenmode spectrum of confined multiferroic. In particular, we demonstrate that the control over the dynamic magnetization and themore » transformation of spatial profiles of transverse modes in magnetic film of the bilayer structure can be performed by the tuning of the wavevectors of transverse modes. The studied confined multiferroic stripe can be utilized for fabrication of integrated dual tunable functional devices for magnonic applications.« less

Method of making organic light emitting devices

DOEpatents

Shiang, Joseph John [Niskayuna, NY; Janora, Kevin Henry [Schenectady, NY; Parthasarathy, Gautam [Saratoga Springs, NY; Cella, James Anthony [Clifton Park, NY; Chichak, Kelly Scott [Clifton Park, NY

2011-03-22

The present invention provides a method for the preparation of organic light-emitting devices comprising a bilayer structure made by forming a first film layer comprising an electroactive material and an INP precursor material, and exposing the first film layer to a radiation source under an inert atmosphere to generate an interpenetrating network polymer composition comprising the electroactive material. At least one additional layer is disposed on the reacted first film layer to complete the bilayer structure. The bilayer structure is comprised within an organic light-emitting device comprising standard features such as electrodes and optionally one or more additional layers serving as a bipolar emission layer, a hole injection layer, an electron injection layer, an electron transport layer, a hole transport layer, exciton-hole transporting layer, exciton-electron transporting layer, a hole transporting emission layer, or an electron transporting emission layer.

Magnetism and electronic structure of (001)- and (111)-oriented LaTiO3 bilayers sandwiched in LaScO3 barriers

NASA Astrophysics Data System (ADS)

Weng, Yakui; Dong, Shuai

2015-05-01

In this study, the magnetism and electronic structure of LaTiO3 bilayers along both the (001) and (111) orientations are calculated using the density functional theory. The band insulator LaScO3 is chosen as the barrier layer and substrate to obtain the isolating LaTiO3 bilayer. For both the (001)- and (111)-oriented cases, LaTiO3 demonstrates the G-type antiferromagnetism as the ground state, similar to the bulk material. However, the electronic structure is significantly changed. The occupied bands of Ti are much narrower in the (111) case, giving a nearly flat band. As a result, the exchange coupling between nearest-neighbor Ti ions is reformed in these superlattices, which will affect the Néel temperature significantly.

Interplay of local structure, charge, and spin in bilayered manganese perovskites

NASA Astrophysics Data System (ADS)

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz; Kapusta, Czesław; Mitchell, John F.

2018-03-01

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. Here, we show results of high-energy resolution x-ray absorption and emission spectroscopies on a La2 -2 xSr1 +2 xMn2O7 family of bilayered manganites in a broad doping range (0.5 ≤x ≤1 ). We established a relation between local Mn charge and Mn-O distances as a function of doping. Based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.

Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richter, Andrew; Dergunov, Sergey; Ganus, Bill

2011-01-01

Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scatteringmore » (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.« less

Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richter, Andrew G.; Dergunov, Sergey A.; Ganus, Bill

2011-03-10

Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scatteringmore » (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Finally, pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.« less

Application of scanning angle Raman spectroscopy for determining the location of buried polymer interfaces with tens of nanometer precision

DOE PAGES

Damin, Craig A.; Nguyen, Vy H. T.; Niyibizi, Auguste S.; ...

2015-02-11

In this study, near-infrared scanning angle (SA) Raman spectroscopy was utilized to determine the interface location in bilayer films (a stack of two polymer layers) of polystyrene (PS) and polycarbonate (PC). Finite-difference-time-domain (FDTD) calculations of the sum square electric field (SSEF) for films with total bilayer thicknesses of 1200–3600 nm were used to construct models for simultaneously measuring the film thickness and the location of the buried interface between the PS and PC layers. Samples with total thicknesses of 1320, 1890, 2300, and 2750 nm and varying PS/PC interface locations were analyzed using SA Raman spectroscopy. Comparing SA Raman spectroscopymore » and optical profilometry measurements, the average percent difference in the total bilayer thickness was 2.0% for films less than ~2300 nm thick. The average percent difference in the thickness of the PS layer, which reflects the interface location, was 2.5% when the PS layer was less than ~1800 nm. SA Raman spectroscopy has been shown to be a viable, non-destructive method capable of determining the total bilayer thickness and buried interface location for bilayer samples consisting of thin polymer films with comparable indices of refraction.« less

Photoluminescent lanthanide-organic bilayer networks with 2,3-pyrazinedicarboxylate and oxalate.

PubMed

Soares-Santos, Paula C R; Cunha-Silva, Luís; Paz, Filipe A Almeida; Ferreira, Rute A S; Rocha, João; Carlos, Luís D; Nogueira, Helena I S

2010-04-05

The hydrothermal reaction between lanthanide nitrates and 2,3-pyrazinedicarboxylic acid led to a new series of two-dimensional (2D) lanthanide-organic frameworks: [Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)](n) [where 2,3-pzdc(2-) = 2,3-pyrazinedicarboxylate, ox(2-) = oxalate, and Ln(III) = Ce, Nd, Sm, Eu, Gd, Tb, or Er]. The structural details of these materials were determined by single-crystal X-ray diffraction (for Ce(3+) and Nd(3+)) that revealed the formation of a layered structure. Cationic monolayers of {(infinity)(2)[Ln(2,3-pzdc)(H(2)O)](+)} are interconnected via the ox(2-) ligand leading to the formation of neutral (infinity)(2)[Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)] bilayer networks; structural cohesion of the crystalline packing is reinforced by the presence of highly directional O-H...O hydrogen bonds between adjacent bilayers. Under the employed hydrothermal conditions 2,3-pyrazinedicarboxylic acid can be decomposed into ox(2-) and 2-pyrazinecarboxylate (2-pzc(-)), as unequivocally proved by the isolation of the discrete complex [Tb(2)(2-pzc)(4)(ox)(H(2)O)(6)].10H(2)O. Single-crystal X-ray diffraction of this latter complex revealed its co-crystallization with an unprecedented (H(2)O)(16) water cluster. Photoluminescence measurements were performed for the Nd(3+), Sm(3+), Eu(3+), and Tb(3+) compounds which show, under UV excitation at room temperature, the Ln(3+) characteristic intra-4f(N) emission peaks. The energy level of the triplet states of 2,3-pyrazinedicarboxylic acid (18939 cm(-1)) and oxalic acid (24570 cm(-1)) was determined from the 12 K emission spectrum of the Gd(3+) compound. The (5)D(0) and (5)D(4) lifetime values (0.333 +/- 0.006 and 0.577 +/- 0.017 ms) and the absolute emission quantum yields (0.13 +/- 0.01 and 0.05 +/- 0.01) were determined for the Eu(3+) and Tb(3+) compounds, respectively. For the Eu(3+) compound the energy transfer efficiency arising from the ligands' excited states was estimated (0.93 +/- 0.01).

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

Consequences of ions and pH on the supramolecular organization of sphingomyelin and sphingomyelin/cholesterol bilayers.

PubMed

Chemin, Caroline; Bourgaux, Claudie; Péan, Jean-Manuel; Pabst, Georg; Wüthrich, Patrick; Couvreur, Patrick; Ollivon, Michel

2008-06-01

For drug delivery purpose the anticancer drug S12363 was loaded into ESM/Chol-liposomes using either a pH or an ammonium gradient. Association between the drug and the liposome depends markedly on the liposome membrane structure. Thus, ESM and ESM/Chol bilayer organization had been characterized by coupled DSC and XRDT as a function of both cholesterol concentration and aqueous medium composition. ESM bilayers exhibited a ripple lamellar gel phase P(beta') below the melting temperature and adopted a L(beta)-like gel phase upon Chol insertion. Supramolecular organization of ESM and ESM/Chol bilayers was not modified by citrate buffer or ammonium sulfate solution whatever the pH (3< or = pH < or =7). Nevertheless, in ESM bilayer, ammonium sulfate salt induced a peculiar organization of head groups, leading to irregular d-spacing and weakly correlated bilayers. Moreover, in the presence of salts, a weakening of van der Waals attraction forces was seen and led to a swelling of the water layer.

Revealing the preferred interlayer orientations and stackings of two-dimensional bilayer gallium selenide crystals.

PubMed

Li, Xufan; Basile, Leonardo; Yoon, Mina; Ma, Cheng; Puretzky, Alexander A; Lee, Jaekwang; Idrobo, Juan C; Chi, Miaofang; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

2015-02-23

Characterizing and controlling the interlayer orientations and stacking orders of two-dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor-phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA' and AB stacking) in as-grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga-terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strain, stabilities and electronic properties of hexagonal BN bilayers

NASA Astrophysics Data System (ADS)

Fujimoto, Yoshitaka; Saito, Susumu

Hexagonal boron nitride (h-BN) atomic layers have been regarded as fascinating materials both scientifically and technologically due to the sizable band gap. This sizable band-gap nature of the h-BN atomic layers would provide not only new physical properties but also novel nano- and/or opto-electronics applications. Here, we study the first-principles density-functional study that clarifies the biaxial strain effects on the energetics and the electronic properties of h-BN bilayers. We show that the band gaps of the h-BN bilayers are tunable by applying strains. Furthermore, we show that the biaxial strains can produce a transition from indirect to direct band gaps of the h-BN bilayer. We also discuss that both AA and AB stacking patterns of h-BN bilayer become feasible structures because h-BN bilayers possess two different directions in the stacking patterns. Supported by MEXT Elements Strategy Initiative to Form Core Research Center through Tokodai Institute for Element Strategy, JSPS KAKENHI Grant Numbers JP26390062 and JP25107005.

The cytosolic domain of T-cell receptor ζ associates with membranes in a dynamic equilibrium and deeply penetrates the bilayer.

PubMed

Zimmermann, Kerstin; Eells, Rebecca; Heinrich, Frank; Rintoul, Stefanie; Josey, Brian; Shekhar, Prabhanshu; Lösche, Mathias; Stern, Lawrence J

2017-10-27

Interactions between lipid bilayers and the membrane-proximal regions of membrane-associated proteins play important roles in regulating membrane protein structure and function. The T-cell antigen receptor is an assembly of eight single-pass membrane-spanning subunits on the surface of T lymphocytes that initiates cytosolic signaling cascades upon binding antigens presented by MHC-family proteins on antigen-presenting cells. Its ζ-subunit contains multiple cytosolic immunoreceptor tyrosine-based activation motifs involved in signal transduction, and this subunit by itself is sufficient to couple extracellular stimuli to intracellular signaling events. Interactions of the cytosolic domain of ζ (ζ cyt ) with acidic lipids have been implicated in the initiation and regulation of transmembrane signaling. ζ cyt is unstructured in solution. Interaction with acidic phospholipids induces structure, but its disposition when bound to lipid bilayers is controversial. Here, using surface plasmon resonance and neutron reflection, we characterized the interaction of ζ cyt with planar lipid bilayers containing mixtures of acidic and neutral lipids. We observed two binding modes of ζ cyt to the bilayers in dynamic equilibrium: one in which ζ cyt is peripherally associated with lipid headgroups and one in which it penetrates deeply into the bilayer. Such an equilibrium between the peripherally bound and embedded forms of ζ cyt apparently controls accessibility of the immunoreceptor tyrosine-based activation signal transduction pathway. Our results reconcile conflicting findings of the ζ structure reported in previous studies and provide a framework for understanding how lipid interactions regulate motifs to tyrosine kinases and may regulate the T-cell antigen receptor biological activities for this cell-surface receptor system.

Breathable NIPAAm Network with Controllable Hydration Supports Model Lipid Membrane

NASA Astrophysics Data System (ADS)

Jablin, Michael; Smith, Hillary; Zhernenkov, Mikhail; Vidyasagar, Ajay; Toomey, Ryan; Saiz, Jessica; Toperverg, Boris; Watkins, Erik; Kuhl, Tonya; Hurd, Alan; Majewski, Jaroslaw

2009-03-01

The interaction of a model lipid bilayer composed of DPPC with a surface-tethered poly(N-isopropylacrylamide) (NIPAAm) was explored with neutron reflectometry (NR). The Langmuir-Blodgett / Langmuir-Schaeffer method was used to deposit a lipid bilayer onto the polymer. NR measurements were used to probe the in- and out-of-plane structure of the system as a function of temperature. NR with fluorescence microscopy show that the polymer supports a lipid bilayer, and hydration of the support can be controlled. At low temp. the membrane develops out-of-plane undulations visible in off-specular scattering. Analysis of the off-specular reveals in-plane correlation of the bilayer fluctuations. The separation of the lipid bilayer from the solid support of a substrate constitutes a significant step towards a more realistic model of biological membranes.

Alcohol's Effects on Lipid Bilayer Properties

PubMed Central

Ingólfsson, Helgi I.; Andersen, Olaf S.

2011-01-01

Alcohols are known modulators of lipid bilayer properties. Their biological effects have long been attributed to their bilayer-modifying effects, but alcohols can also alter protein function through direct protein interactions. This raises the question: Do alcohol's biological actions result predominantly from direct protein-alcohol interactions or from general changes in the membrane properties? The efficacy of alcohols of various chain lengths tends to exhibit a so-called cutoff effect (i.e., increasing potency with increased chain length, which that eventually levels off). The cutoff varies depending on the assay, and numerous mechanisms have been proposed such as: limited size of the alcohol-protein interaction site, limited alcohol solubility, and a chain-length-dependent lipid bilayer-alcohol interaction. To address these issues, we determined the bilayer-modifying potency of 27 aliphatic alcohols using a gramicidin-based fluorescence assay. All of the alcohols tested (with chain lengths of 1–16 carbons) alter the bilayer properties, as sensed by a bilayer-spanning channel. The bilayer-modifying potency of the short-chain alcohols scales linearly with their bilayer partitioning; the potency tapers off at higher chain lengths, and eventually changes sign for the longest-chain alcohols, demonstrating an alcohol cutoff effect in a system that has no alcohol-binding pocket. PMID:21843475

Electrochemical measurement of lateral diffusion coefficients of ubiquinones and plastoquinones of various isoprenoid chain lengths incorporated in model bilayers.

PubMed Central

Marchal, D; Boireau, W; Laval, J M; Moiroux, J; Bourdillon, C

1998-01-01

The long-range diffusion coefficients of isoprenoid quinones in a model of lipid bilayer were determined by a method avoiding fluorescent probe labeling of the molecules. The quinone electron carriers were incorporated in supported dimyristoylphosphatidylcholine layers at physiological molar fractions (<3 mol%). The elaborate bilayer template contained a built-in gold electrode at which the redox molecules solubilized in the bilayer were reduced or oxidized. The lateral diffusion coefficient of a natural quinone like UQ10 or PQ9 was 2.0 +/- 0.4 x 10(-8) cm2 s(-1) at 30 degrees C, two to three times smaller than the diffusion coefficient of a lipid analog in the same artificial bilayer. The lateral mobilities of the oxidized or reduced forms could be determined separately and were found to be identical in the 4-13 pH range. For a series of isoprenoid quinones, UQ2 or PQ2 to UQ10, the diffusion coefficient exhibited a marked dependence on the length of the isoprenoid chain. The data fit very well the quantitative behavior predicted by a continuum fluid model in which the isoprenoid chains are taken as rigid particles moving in the less viscous part of the bilayer and rubbing against the more viscous layers of lipid heads. The present study supports the concept of a homogeneous pool of quinone located in the less viscous region of the bilayer. PMID:9545054

Organization and dynamics of pyrene and pyrene lipids in intact lipid bilayers. Photo-induced charge transfer processes.

PubMed Central

Barenholz, Y; Cohen, T; Korenstein, R; Ottolenghi, M

1991-01-01

The dynamics of fluorescence quenching and the organization of a series of pyrene derivatives anchored in various depths in bilayers of phosphatidylcholine small unilamellar vesicles was studied and compared with their behavior in homogeneous solvent systems. The studies include characterization of the environmental polarity of the pyrene fluorophore based on its vibronic peaks, as well as the interaction with three collisional quenchers: the two membrane-soluble quenchers, diethylaniline and bromobenzene, and the water soluble quencher potassium iodide. The system of diethylaniline-pyrene derivatives in the membrane of phosphatidylcholine vesicles was characterized in detail. The diethylaniline partition coefficient between the lipid bilayers and the buffer is approximately 5,800. Up to a diethylaniline/phospholipid mole ratio of 1:3 the perturbation to membrane structure is minimal so that all photophysical studies were performed below this mole ratio. The quenching reaction, in all cases, was shown to take place in the lipid bilayer interior and the relative quenching efficiencies of the various probe molecules was used to provide information on the distribution of both fluorescent probes and quencher molecules in the lipid bilayer. The quenching efficiency by diethylaniline in the lipid bilayer was found to be essentially independent on the length of the methylene chain of the pyrene moiety. These findings suggest that the quenching process, being a diffusion controlled reaction, is determined by the mobility of the diethylaniline quencher (with an effective diffusion coefficient D approximately 10(-7) cm2 s-1) which appears to be homogeneously distributed throughout the lipid bilayer. The pulsed laser photolysis products of the charge-transfer quenching reaction were examined. No exciplex (excited-complex) formation was observed and the yield of the separated radical ions was shown to be tenfold smaller than in homogenous polar solutions. The decay of the radical ions is considerably faster than the corresponding process in homogenous solutions. Relatively high intersystem crossing yields are observed. The results are explained on the basis of the intrinsic properties of a lipid bilayer, primarily, its rigid spatial organization. It is suggested that such properties favor ion-pair formation over exciplex generation. They also enhance primary geminate recombination of initially formed (solvent-shared) ion pairs. Triplet states are generated via secondary geminate recombination of ion pairs in the membrane interior. The results bear on the general mechanism of electron transfer processes in biomembranes. PMID:1883931

Effect of Cholesterol on the Structure of a Five-Component Mitochondria-Like Phospholipid Membrane

PubMed Central

Cathcart, Kelly; Patel, Amit; Dies, Hannah; Rheinstädter, Maikel C.; Fradin, Cécile

2015-01-01

Cellular membranes have a complex phospholipid composition that varies greatly depending on the organism, cell type and function. In spite of this complexity, most structural data available for phospholipid bilayers concern model systems containing only one or two different phospholipids. Here, we examine the effect of cholesterol on the structure of a complex membrane reflecting the lipid composition of mitochondrial membranes, with five different types of headgroups (phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylinositol (PI), phosphatidylserine (PS) and cardiolipin (CL)) and a variety of hydrocarbon tails. This particular system was chosen because elevated cholesterol contents in mitochondrial membranes have been linked to a breaking down of Bax-mediated membrane permeabilization and resistance to cancer treatments. High resolution electron density profiles were determined by X-ray reflectivity, while the area per phospholipid chain, Apc, and the chain order parameter, SX-ray, were determined by wide-angle X-ray scattering (WAXS). We show that chain order increases upon the addition of cholesterol, resulting in both a thickening of the lipid bilayer and a reduction in the average surface area per phospholipid chain. This effect, well known as cholesterol’s condensation effect, is similar, but not as pronounced as for single-component phospholipid membranes. We conclude by discussing the relevance of these findings for the insertion of the pro-apoptotic protein Bax in mitochondrial membranes with elevated cholesterol content. PMID:26529029

Effect of Cholesterol on the Structure of a Five-Component Mitochondria-Like Phospholipid Membrane.

PubMed

Cathcart, Kelly; Patel, Amit; Dies, Hannah; Rheinstädter, Maikel C; Fradin, Cécile

2015-10-30

Cellular membranes have a complex phospholipid composition that varies greatly depending on the organism, cell type and function. In spite of this complexity, most structural data available for phospholipid bilayers concern model systems containing only one or two different phospholipids. Here, we examine the effect of cholesterol on the structure of a complex membrane reflecting the lipid composition of mitochondrial membranes, with five different types of headgroups (phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylinositol (PI), phosphatidylserine (PS) and cardiolipin (CL)) and a variety of hydrocarbon tails. This particular system was chosen because elevated cholesterol contents in mitochondrial membranes have been linked to a breaking down of Bax-mediated membrane permeabilization and resistance to cancer treatments. High resolution electron density profiles were determined by X-ray reflectivity, while the area per phospholipid chain, Apc, and the chain order parameter, SX-ray, were determined by wide-angle X-ray scattering (WAXS). We show that chain order increases upon the addition of cholesterol, resulting in both a thickening of the lipid bilayer and a reduction in the average surface area per phospholipid chain. This effect, well known as cholesterol's condensation effect, is similar, but not as pronounced as for single-component phospholipid membranes. We conclude by discussing the relevance of these findings for the insertion of the pro-apoptotic protein Bax in mitochondrial membranes with elevated cholesterol content.

Surfactant-assisted growth and optical properties of ZnO hexagonal bilayer disk-like microstructures

NASA Astrophysics Data System (ADS)

Zhu, Q. P.; Shen, X. Y.; Wang, L. L.; Zhu, L. P.; Wang, L. J.; Liao, G. H.

2018-01-01

ZnO hexagonal bilayer disk-like microstructures are successfully fabricated using a simple solvothermal method assisted with surfactant. The structure and morphology were investigated by XRD, SEM, and EDS. XRD result indicated that the as-obtained samples were well-crystallized wurtzite hexagonal ZnO structure. SEM images showed that the ZnO hexagonal bilayer disk-like assembles consist of two uniform and smooth disks with an average edge length of 6 μm and thickness of ˜4 μm. UV-vis spectrum reveals that ZnO sampls show an appreciable red shift and the band gap energy of the obtained ZnO samples were about 3.15 eV. A very strong UV emission at the ultraviolet (UV) region was observed in the photoluminescence (PL) spectrum of the as-prepared ZnO samples tested at room-temperature. A possible growth process of the ZnO hexagonal bilayer disk-like microstructures was schematically illustrated.

A modular platform for one-step assembly of multi-component membrane systems by fusion of charged proteoliposomes

NASA Astrophysics Data System (ADS)

Ishmukhametov, Robert R.; Russell, Aidan N.; Berry, Richard M.

2016-10-01

An important goal in synthetic biology is the assembly of biomimetic cell-like structures, which combine multiple biological components in synthetic lipid vesicles. A key limiting assembly step is the incorporation of membrane proteins into the lipid bilayer of the vesicles. Here we present a simple method for delivery of membrane proteins into a lipid bilayer within 5 min. Fusogenic proteoliposomes, containing charged lipids and membrane proteins, fuse with oppositely charged bilayers, with no requirement for detergent or fusion-promoting proteins, and deliver large, fragile membrane protein complexes into the target bilayers. We demonstrate the feasibility of our method by assembling a minimal electron transport chain capable of adenosine triphosphate (ATP) synthesis, combining Escherichia coli F1Fo ATP-synthase and the primary proton pump bo3-oxidase, into synthetic lipid vesicles with sizes ranging from 100 nm to ~10 μm. This provides a platform for the combination of multiple sets of membrane protein complexes into cell-like artificial structures.

Structural and electronic transformation in low-angle twisted bilayer graphene

NASA Astrophysics Data System (ADS)

Gargiulo, Fernando; Yazyev, Oleg V.

2018-01-01

Experiments on bilayer graphene unveiled a fascinating realization of stacking disorder where triangular domains with well-defined Bernal stacking are delimited by a hexagonal network of strain solitons. Here we show by means of numerical simulations that this is a consequence of a structural transformation of the moiré pattern inherent to twisted bilayer graphene taking place at twist angles θ below a crossover angle θ\\star=1.2\\circ . The transformation is governed by the interplay between the interlayer van der Waals interaction and the in-plane strain field, and is revealed by a change in the functional form of the twist energy density. This transformation unveils an electronic regime characteristic of vanishing twist angles in which the charge density converges, though not uniformly, to that of ideal bilayer graphene with Bernal stacking. On the other hand, the stacking domain boundaries form a distinct charge density pattern that provides the STM signature of the hexagonal solitonic network.

Revealing the preferred interlayer orientations and stackings of two-dimensional bilayer gallium selenide crystals

DOE PAGES

Li, Xufan; Basile Carrasco, Leonardo A.; Yoon, Mina; ...

2015-01-21

Characterizing and controlling the interlayer orientations and stacking order of bilayer two-dimensional (2D) crystals and van der Waals (vdW) heterostructure is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) that result from different layer stacking provide an ideal platform to study the stacking configurations in bilayer 2D crystals. Here, through a controllable vapor-phase deposition method we selectively grow bilayer GaSe crystals and investigate their two preferred 0° or 60° interlayer rotations. The commensurate stacking configurations (AA' and AB-stacking) in as-grown 2D bilayer GaSe crystals are clearly observed at the atomic scale andmore » the Ga-terminated edge structure are identified for the first time by using atomic-resolution scanning transmission electron microscopy (STEM). Theoretical analysis of the interlayer coupling energetics vs. interlayer rotation angle reveals that the experimentally-observed orientations are energetically preferred among the bilayer GaSe crystal polytypes. Here, the combined experimental and theoretical characterization of the GaSe bilayers afforded by these growth studies provide a pathway to reveal the atomistic relationships in interlayer orientations responsible for the electronic and optical properties of bilayer 2D crystals and vdW heterostructures.« less

Effect of Alcohol on Interaction of Model Biological Membrane with Steroids

NASA Astrophysics Data System (ADS)

Pinna, Marco; Mura, Manuela; Famili, Marjan; Zhou, Yuhua; Zvelindovsky, Andrei

2014-03-01

The effect of alcohol in the lipid bilayer changes the gel-phase structure of the lipid bilayer. Interactions between the alcohol molecules and the lipid bilayer were investigated using molecular dynamics. Alcohols such as ethanol and methanol are often used in drug delivery application. Ethanol is used to dissolve hydrophobic steroidal drugs such as Beclamethasone dipropionate, Fluticasone propionate and Prednisone. All the systems considered were equilibrated at 310K and ran for 100ns in the presence of dimyristoylphosphatidylcholine (DMPC) lipid bilayer. In addition the simulations were performed to investigate the behaviour of anti-asthma drugs such as Beclamethasone dipropionate in the water environment and 2.5% of ethanol.

Membrane Protein Incorporation into Nano-Bioelectronics: An insight into Rhodopsin Controlled SiNW-FET Devices

NASA Astrophysics Data System (ADS)

Tunuguntla, Ramya

Biological systems use different energy sources to interact with their environments by creating ion gradients, membrane electric potentials, or a proton motive force to accomplish strikingly complex tasks on the nanometer length scale, such as energy harvesting, and whole organism replication. Most of this activity involves a vast arsenal of active and passive ion channels, membrane receptors and ion pumps that mediate complex and precise transport across biological membranes. Despite the remarkable rate of progress exhibited by modern microelectronic devices, they still cannot compete with the efficiency and precision of biological systems on the component level. At the same time, the sophistication of these molecular machines provides an excellent opportunity to use them in hybrid bioelectronic devices where such a combination could deliver enhanced electronic functionality and enable seamless bi-directional interfaces between man-made and biological assemblies. Artificial membrane systems allow researchers to study the structure and function of membrane proteins in a matrix that approximates their natural environment and to integrate these proteins in ex-vivo devices such as electronic biosensors, thin-film protein arrays, or bio-fuel cells. Since most membrane proteins have vectorial functions, both functional studies and applications require effective control over protein orientation within a lipid bilayer. In our work, we have explored the role of the bilayer surface charge in determining transmembrane protein orientation and functionality during formation of proteoliposomes. We reconstituted a model vectorial ion pump, proteorhodopsin, in liposomes of opposite charges and varying charge densities and determined the resultant protein orientation. Antibody-binding assay and proteolysis of proteoliposomes showed physical evidence of preferential orientation, and functional assays verified vectorial nature of ion transport in this system. Our results indicate that the manipulation of lipid composition can indeed control orientation of an asymmetrically charged membrane protein, proteorhodopsin, in liposomes. One-dimensional inorganic nanostructures, which have critical dimensions comparable to the sizes of biological molecules, form an excellent materials platform for building such integrated structures. Researchers already use silicon nanowire-based field effect transistors functionalized with molecular recognition sites in a diverse array of biosensors. In our group, we have been developing a platform for integration of membrane protein functionality and electronic devices using a 1-D phospholipid bilayer device architecture. In these devices, the membrane proteins reside within the lipid bilayer that covers a nanowire channel of a field-effect transistor. This lipid bilayer performs several functions: it shields the nanowire from the solution species; it serves as a native-like environment for membrane proteins and preserves their functionality, integrity, and even vectorality. In this work, we show that a 1-D bilayer device incorporating a rhodopsin proton pump allows us to couple light-driven proton transport to a bioelectronic circuit. We also report that we were able to adapt another distinctive feature of biological signal processing---their widespread use of modifiers, co-factors, and mediator molecules---to regulate and fine-tune the operational characteristics of the bioelectronic device. In our example, we use co-assembly of protein channels and ionophores in the 1-D bilayer to modify the device output levels and response time.

Structure and organization of nanosized-inclusion-containing bilayer membranes

NASA Astrophysics Data System (ADS)

Ren, Chun-Lai; Ma, Yu-Qiang

2009-07-01

Based on a considerable amount of experimental evidence for lateral organization of lipid membranes which share astonishingly similar features in the presence of different inclusions, we use a hybrid self-consistent field theory (SCFT)/density-functional theory (DFT) approach to deal with bilayer membranes embedded by nanosized inclusions and explain experimental findings. Here, the hydrophobic inclusions are simple models of hydrophobic drugs or other nanoparticles for biomedical applications. It is found that lipid/inclusion-rich domains are formed at moderate inclusion concentrations and disappear with the increase in the concentration of inclusions. At high inclusion content, chaining of inclusions occurs due to the effective depletion attraction between inclusions mediated by lipids. Meanwhile, the increase in the concentration of inclusions can also cause thickening of the membrane and the distribution of inclusions undergoes a layering transition from one-layer structure located in the bilayer midplane to two-layer structure arranged into the two leaflets of a bilayer. Our theoretical predictions address the complex interactions between membranes and inclusions suggesting a unifying mechanism which reflects the competition between the conformational entropy of lipids favoring the formation of lipid- and inclusion-rich domains in lipids and the steric repulsion of inclusions leading to the uniform dispersion.

Structure and tribological behavior of Pb-Ti/MoS2 nanoscaled multilayer films deposited by magnetron sputtering method

NASA Astrophysics Data System (ADS)

Li, Hao; Xie, Mingling; Zhang, Guangan; Fan, Xiaoqiang; Li, Xia; Zhu, Minhao; Wang, Liping

2018-03-01

The Pb-Ti/MoS2 nanoscaled multilayer films with different bilayer period were deposited by unbalanced magnetron sputtering system. The morphology, microstructure, mechanical and tribological properties of the films were investigated. It was found that the film changed from multilayer structure to composite structure as the bilayer period decreased from 25 nm to 6 nm, due to the diffusion effect. The multilayer film showed a pronounced (002) diffraction peak, the growth of the MoS2 platelets below the interface were affected by Pb and Ti, and the c-axis of MoS2 platelets were inclined to the substrate at an angle of -30° to 30°. The hardness of the film ranged from 5.9 to 7.2 GPa depending on the bilayer period. The tribological behavior of the films was performed under vacuum, and the friction coefficient were typically below 0.25. Furthermore, the nanoscale multilayer film with a bilayer period of 20 nm exhibits much better mechanical and tribological properties than pure MoS2. The result indicates that the nanoscale multilayer is a design methodology for developing high basal plane oriented and vacuum solid lubricating MoS2 based materials.

Structured Water Layers Adjacent to Biological Membranes

PubMed Central

Higgins, Michael J.; Polcik, Martin; Fukuma, Takeshi; Sader, John E.; Nakayama, Yoshikazu; Jarvis, Suzanne P.

2006-01-01

Water amid the restricted space of crowded biological macromolecules and at membrane interfaces is essential for cell function, though the structure and function of this “biological water” itself remains poorly defined. The force required to remove strongly bound water is referred to as the hydration force and due to its widespread importance, it has been studied in numerous systems. Here, by using a highly sensitive dynamic atomic force microscope technique in conjunction with a carbon nanotube probe, we reveal a hydration force with an oscillatory profile that reflects the removal of up to five structured water layers from between the probe and biological membrane surface. Further, we find that the hydration force can be modified by changing the membrane fluidity. For 1,2-dipalmitoyl-sn-glycero-3-phosphocholine gel (Lβ) phase bilayers, each oscillation in the force profile indicates the force required to displace a single layer of water molecules from between the probe and bilayer. In contrast, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine fluid (Lα) phase bilayers at 60°C and 1,2-dioleoyl-sn-glycero-3-phosphocholine fluid (Lα) phase bilayers at 24°C seriously disrupt the molecular ordering of the water and result predominantly in a monotonic force profile. PMID:16798815

Two-dimensional silica opens new perspectives

NASA Astrophysics Data System (ADS)

Büchner, Christin; Heyde, Markus

2017-12-01

In recent years, silica films have emerged as a novel class of two-dimensional (2D) materials. Several groups succeeded in epitaxial growth of ultrathin SiO2 layers using different growth methods and various substrates. The structures consist of tetrahedral [SiO4] building blocks in two mirror symmetrical planes, connected via oxygen bridges. This arrangement is called a silica bilayer as it is the thinnest 2D arrangement with the stoichiometry SiO2 known today. With all bonds saturated within the nano-sheet, the interaction with the substrate is based on van der Waals forces. Complex ring networks are observed, including hexagonal honeycomb lattices, point defects and domain boundaries, as well as amorphous domains. The network structures are highly tuneable through variation of the substrate, deposition parameters, cooling procedure, introducing dopants or intercalating small species. The amorphous networks and structural defects were resolved with atomic resolution microscopy and modeled with density functional theory and molecular dynamics. Such data contribute to our understanding of the formation and characteristic motifs of glassy systems. Growth studies and doping with other chemical elements reveal ways to tune ring sizes and defects as well as chemical reactivities. The pristine films have been utilized as molecular sieves and for confining molecules in nanocatalysis. Post growth hydroxylation can be used to tweak the reactivity as well. The electronic properties of silica bilayers are favourable for using silica as insulators in 2D material stacks. Due to the fully saturated atomic structure, the bilayer interacts weakly with the substrate and can be described as quasi-freestanding. Recently, a mm-scale film transfer under structure retention has been demonstrated. The chemical and mechanical stability of silica bilayers is very promising for technological applications in 2D heterostacks. Due to the impact of this bilayer system for glass science, catalysis and the field of 2D materials, a large number of theoretical and experimental studies on silica bilayers have been reported in the last years. This review aims to provide an overview on the insights gained on this material and to point out opportunities for further discovery in various fields.

Enhanced sensitivity of a microfabricated resonator using a graphene-polystyrene bilayer membrane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yun, Minhyuk; Lee, Eunho; Cho, Kilwon

2014-08-18

A graphene layer was synthesized using chemical vapor deposition methods and a polystyrene solution was spin-cast onto the graphene film. The graphene-polystyrene bilayer membrane was attached between the two tines of a microfabricated quartz tuning fork (QTF). The modulus of the graphene-polystyrene bilayer was measured to be twice that of a pristine polystyrene membrane. Exposure of the membrane-coated QTF to ethanol vapor decreased the resonance frequency of the microresonator. The bilayer membrane-coated QTF produced a frequency change that was three times the change obtained using a polystyrene membrane-coated QTF, with a lower degree of degradation in the Q factor. Themore » limit of detection of the bilayer membrane-coated QTF to ethanol vapor was determined to be 20 ppm.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Sang Wan; Lee, Sangho; Kim, Minsoo

The interfacial electronic structure of a bilayer of chloroaluminum phthalocyanine (ClAlPc) and pentacene grown on indium tin oxide (ITO) has been studied using synchrotron-radiation-excited photoelectron spectroscopy. The energy difference between the highest occupied molecular orbital (HOMO) level of the pentacene layer and the lowest unoccupied molecular orbital (LUMO) level of the ClAlPc layer (E HOMO D - E LUMO A ) was determined and compared with that of C 60/pentacene bilayers. The E HOMO D - E LUMO A of a heterojunction with ClAlPc was found to be 1.3 eV while that with C 60 was 0.9 eV. This differencemore » is discussed in terms of the difference in the ionization energy of each acceptor materials. We also obtained the complete energy level diagrams of both ClAlPc/pentacene/ITO and C 60/pentacene/ITO.« less

Temperature dependence of structure, bending rigidity, and bilayer interactions of dioleoylphosphatidylcholine bilayers.

PubMed

Pan, Jianjun; Tristram-Nagle, Stephanie; Kucerka, Norbert; Nagle, John F

2008-01-01

X-ray diffuse scattering was measured from oriented stacks and unilamellar vesicles of dioleoylphosphatidylcholine lipid bilayers to obtain the temperature dependence of the structure and of the material properties. The area/molecule, A, was 75.5 A(2) at 45 degrees C, 72.4 A(2) at 30 degrees C, and 69.1 A(2) at 15 degrees C, which gives the area expansivity alpha(A) = 0.0029/deg at 30 degrees C, and we show that this value is in excellent agreement with the polymer brush theory. The bilayer becomes thinner with increasing temperature; the contractivity of the hydrocarbon portion was alpha(Dc) = 0.0019/deg; the difference between alpha(A) and alpha(Dc) is consistent with the previously measured volume expansivity alpha(Vc) = 0.0010/deg. The bending modulus K(C) decreased as exp(455/T) with increasing T (K). Our area compressibility modulus K(A) decreased with increasing temperature by 5%, the same as the surface tension of dodecane/water, in agreement again with the polymer brush theory. Regarding interactions between bilayers, the compression modulus B as a function of interbilayer water spacing D'(W) was found to be nearly independent of temperature. The repulsive fluctuation pressure calculated from B and K(C) increased with temperature, and the Hamaker parameter for the van der Waals interaction was nearly independent of temperature; this explains why the fully hydrated water spacing, D'(W), that we obtain from our structural results increases with temperature.

Critical Nucleus Structure and Aggregation Mechanism of the C-terminal Fragment of Copper-Zinc Superoxide Dismutase Protein.

PubMed

Zou, Yu; Sun, Yunxiang; Zhu, Yuzhen; Ma, Buyong; Nussinov, Ruth; Zhang, Qingwen

2016-03-16

The aggregation of the copper-zinc superoxide dismutase (SOD1) protein is linked to familial amyotrophic lateral sclerosis, a progressive neurodegenerative disease. A recent experimental study has shown that the (147)GVIGIAQ(153) SOD1 C-terminal segment not only forms amyloid fibrils in isolation but also accelerates the aggregation of full-length SOD1, while substitution of isoleucine at site 149 by proline blocks its fibril formation. Amyloid formation is a nucleation-polymerization process. In this study, we investigated the oligomerization and the nucleus structure of this heptapeptide. By performing extensive replica-exchange molecular dynamics (REMD) simulations and conventional MD simulations, we found that the GVIGIAQ hexamers can adopt highly ordered bilayer β-sheets and β-barrels. In contrast, substitution of I149 by proline significantly reduces the β-sheet probability and results in the disappearance of bilayer β-sheet structures and the increase of disordered hexamers. We identified mixed parallel-antiparallel bilayer β-sheets in both REMD and conventional MD simulations and provided the conformational transition from the experimentally observed parallel bilayer sheets to the mixed parallel-antiparallel bilayer β-sheets. Our simulations suggest that the critical nucleus consists of six peptide chains and two additional peptide chains strongly stabilize this critical nucleus. The stabilized octamer is able to recruit additional random peptides into the β-sheet. Therefore, our simulations provide insights into the critical nucleus formation and the smallest stable nucleus of the (147)GVIGIAQ(153) peptide.

Interplay of local structure, charge, and spin in bilayered manganese perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. In this paper, we show results of high-energy resolution x-ray absorption and emission spectroscopies on amore » $${\\mathrm{La}}_{2{-}2x}{\\mathrm{Sr}}_{1+2x}{\\mathrm{Mn}}_{2}{\\mathrm{O}}_{7}$$ family of bilayered manganites in a broad doping range $$(0.5{\\le}x{\\le}1)$$. We established a relation between local Mn charge and Mn-O distances as a function of doping. Finally, based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.« less

Interplay of local structure, charge, and spin in bilayered manganese perovskites

DOE PAGES

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz; ...

2018-03-27

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. In this paper, we show results of high-energy resolution x-ray absorption and emission spectroscopies on amore » $${\\mathrm{La}}_{2{-}2x}{\\mathrm{Sr}}_{1+2x}{\\mathrm{Mn}}_{2}{\\mathrm{O}}_{7}$$ family of bilayered manganites in a broad doping range $$(0.5{\\le}x{\\le}1)$$. We established a relation between local Mn charge and Mn-O distances as a function of doping. Finally, based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.« less

Exploring 3D non-interpenetrated metal-organic framework with malonate-bridged Co(II) coordination polymer: structural elucidation and theoretical study

NASA Astrophysics Data System (ADS)

Hossain, Anowar; Mandal, Tripti; Mitra, Monojit; Manna, Prankrishna; Bauzá, Antonio; Frontera, Antonio; Seth, Saikat Kumar; Mukhopadhyay, Subrata

2017-12-01

A Co(II)-based coordination polymer with tetranuclear cobalt(II)-malonate cluster has been easily generated by aqueous medium self-assembly from Cobalt(II) chloride hexahydrate and malonic acid. The structure exhibits a non-interpenetrating, highly undulating two-dimensional (2D) bi-layer network with (4,4) topology. The crystal structure is composed of infinite interdigitated 2D metal-organic bi-layers which extended to an intricate 3D framework through the interbilayer hydrogen bonds. We have studied energetically by means of Density Functional Theory (DFT) calculations the H-bonding interactions that connect the 2D metal-organic bi-layers. The finite theoretical models have been used to compute conventional O‒H•••O and unconventional C‒H•••O interactions which plays a key role to build 3D architecture.

Role of the array geometry in multi-bilayer hair cell sensors

NASA Astrophysics Data System (ADS)

Tamaddoni, Nima J.; Sarles, Stephen A.

2014-03-01

Recently, a bio-inspired, synthetic membrane-based hair cell sensor was fabricated and characterized. This sensor generates current in response to mechanical stimuli, such as airflow or free vibration, which perturb the sensor's hair. Vibration transferred from the hair to a lipid membrane (lipid bilayer) causes a voltage-dependent time rate of change in electrical capacitance of the membrane, which produces measurable current. Studies to date have been performed on systems containing only two droplets and a single bilayer, even though an array of multiple bilayers can be formed with more than 2 droplets. Thus, it is yet to be determined how multiple lipid bilayers affect the sensing response of a membrane-based hair cell sensor. In this work, we assemble serial droplet arrays with more than 1 bilayer to experimentally study the current generated by each membrane in response to perturbation of a single hair element. Two serial array configurations are studied: The first consists of a serial array of 3 bilayers formed using 4 droplets with the hair positioned in an end droplet. The second configuration consists of 3 droplets and 2 bilayers in series with the hair positioned in the central droplet. In serial arrays of up to four droplets, we observe that mechanotransduction of the hair's motion into a capacitive current occurs at every membrane, with bilayers positioned adjacent to the droplet containing the hair generating the largest sensing current. The measured currents suggest the total current generated by all bilayers in a 4-droplet, 3-bilaye array is greater than the current produced by a single-membrane sensor and similar in magnitude to the sum of currents output by 3, single-bilayer sensors operated independently. Moreover, we learned that bilayers positioned on the same side of the hair produce sensing currents that are in-phase, whereas bilayers positioned on opposite sides of the droplet containing the hair generate out-of-phase responses.

Membrane solubilisation and reconstitution by octylglucoside: comparison of synthetic lipid and natural lipid extract by isothermal titration calorimetry.

PubMed

Krylova, Oxana O; Jahnke, Nadin; Keller, Sandro

2010-08-01

We have studied the solubilisation and reconstitution of lipid membranes composed of either synthetic phosphatidylcholine or Escherichia. coli polar lipid extract by the non-ionic detergent octylglucoside. For both lipid systems, composition-dependent transformations of unilamellar vesicles into micelles or vice versa were followed by high-sensitivity isothermal titration calorimetry. Data obtained over a range of detergent and lipid concentrations could be rationalised in terms of a three-stage phase separation model involving bilayer, bilayer/micelle coexistence, and micellar ranges, yielding the detergent/lipid phase diagrams and the bilayer-to-micelle partition coefficients of both detergent and lipid. The most notable difference between the lipids investigated was a substantial widening of the bilayer/micelle coexistence range for E. coli lipid, which was due to an increased preference of the detergent and a decreased affinity of the lipid for the micellar phase as compared with the bilayer phase. These effects on the bilayer-to-micelle partition coefficients could be explained by the high proportion in E. coli membranes of lipids possessing negative spontaneous curvature, which hampers both their transfer into strongly curved micellar structures as well as the insertion of detergent into condensed bilayers.

Structure refinement of membrane proteins via molecular dynamics simulations.

PubMed

Dutagaci, Bercem; Heo, Lim; Feig, Michael

2018-07-01

A refinement protocol based on physics-based techniques established for water soluble proteins is tested for membrane protein structures. Initial structures were generated by homology modeling and sampled via molecular dynamics simulations in explicit lipid bilayer and aqueous solvent systems. Snapshots from the simulations were selected based on scoring with either knowledge-based or implicit membrane-based scoring functions and averaged to obtain refined models. The protocol resulted in consistent and significant refinement of the membrane protein structures similar to the performance of refinement methods for soluble proteins. Refinement success was similar between sampling in the presence of lipid bilayers and aqueous solvent but the presence of lipid bilayers may benefit the improvement of lipid-facing residues. Scoring with knowledge-based functions (DFIRE and RWplus) was found to be as good as scoring using implicit membrane-based scoring functions suggesting that differences in internal packing is more important than orientations relative to the membrane during the refinement of membrane protein homology models. © 2018 Wiley Periodicals, Inc.

Lipid bilayers: thermodynamics, structure, fluctuations, and interactions.

PubMed

Tristram-Nagle, Stephanie; Nagle, John F

2004-01-01

This article, adapted from our acceptance speech of the Avanti Award in Lipids at the 47th Biophysical Society meeting in San Antonio, 2003, summarizes over 30 years of research in the area of lipid bilayers. Beginning with a theoretical model of the phase transition (J.F.N.), we have proceeded experimentally using dilatometry and density centrifugation to study volume, differential scanning calorimetry to study heat capacity, and X-ray scattering techniques to study structure of lipid bilayers as a function of temperature. Electron density profiles of the gel and ripple phases have been obtained as well as profiles from several fluid phase lipids, which lead to many structural results that compliment molecular dynamics simulations from other groups. Using the theory of liquid crystallography plus oriented lipid samples, we are the first group to obtain both material parameters (KC and B) associated with the fluctuations in fluid phase lipids. This allows us to use fully hydrated lipid samples, as in vivo, to obtain the structure.

New group-V elemental bilayers: A tunable structure model with four-, six-, and eight-atom rings

NASA Astrophysics Data System (ADS)

Kong, Xiangru; Li, Linyang; Leenaerts, Ortwin; Liu, Xiong-Jun; Peeters, François M.

2017-07-01

Two-dimensional group-V elemental materials have attracted widespread attention due to their nonzero band gap while displaying high electron mobility. Using first-principles calculations, we propose a series of new elemental bilayers with group-V elements (Bi, Sb, As). Our study reveals the dynamical stability of four-, six-, and eight-atom ring structures, demonstrating their possible coexistence in such bilayer systems. The proposed structures for Sb and As are large-gap semiconductors that are potentially interesting for applications in future nanodevices. The Bi structures have nontrivial topological properties with a direct nontrivial band gap. The nontrivial gap is shown to arise from a band inversion at the Brillouin zone center due to the strong intrinsic spin-orbit coupling in Bi atoms. Moreover, we demonstrate the possibility of tuning the properties of these materials by enhancing the ratio of six-atom rings to four- and eight-atom rings, which results in wider nontrivial band gaps and lower formation energies.

Lipid bilayers: thermodynamics, structure, fluctuations, and interactions

PubMed Central

Tristram-Nagle, Stephanie; Nagle, John F.

2009-01-01

This article, adapted from our acceptance speech of the Avanti Award in Lipids at the 47th Biophysical Society meeting in San Antonio, 2003, summarizes over 30 years of research in the area of lipid bilayers. Beginning with a theoretical model of the phase transition (J.F.N.), we have proceeded experimentally using dilatometry and density centrifugation to study volume, differential scanning calorimetry to study heat capacity, and X-ray scattering techniques to study structure of lipid bilayers as a function of temperature. Electron density profiles of the gel and ripple phases have been obtained as well as profiles from several fluid phase lipids, which lead to many structural results that compliment molecular dynamics simulations from other groups. Using the theory of liquid crystallography plus oriented lipid samples, we are the first group to obtain both material parameters (KC and B) associated with the fluctuations in fluid phase lipids. This allows us to use fully hydrated lipid samples, as in vivo, to obtain the structure. PMID:14706737

Unconventional fractional quantum Hall effect in monolayer and bilayer graphene

PubMed Central

Jacak, Janusz; Jacak, Lucjan

2016-01-01

The commensurability condition is applied to determine the hierarchy of fractional fillings of Landau levels in monolayer and in bilayer graphene. The filling rates for fractional quantum Hall effect (FQHE) in graphene are found in the first three Landau levels in one-to-one agreement with the experimental data. The presence of even denominator filling fractions in the hierarchy for FQHE in bilayer graphene is explained. Experimentally observed hierarchy of FQHE in the first and second Landau levels in monolayer graphene and in the zeroth Landau level in bilayer graphene is beyond the conventional composite fermion interpretation but fits to the presented nonlocal topology commensurability condition. PMID:27877866

Reversible Lifting of Surface Supported Lipid Bilayers with a Membrane-Spanning Nonionic Triblock Copolymer

DOE PAGES

Hayden, Steven C.; Junghans, Ann; Majewski, Jaroslaw; ...

2017-02-22

Neutron reflectometry was used to monitor structural variations in surface supported DMPC bilayers induced by the addition of Triton X-100, a surfactant commonly used to aid solubilization of membrane proteins, and the co-addition of a membrane spanning non-ionic amphiphilic triblock copolymer, (PEO 117-PPO 47-PE O117, Pluronic F98). Surfactant addition causes slight compression of the bilayer thickness and the creation of a distinct EO layer that increases the hydrophilic layer proximal to the supporting substrate (i.e., a water and EO gap between the lipid bilayer and quartz) to 6.8 ± 0.4 Å. Addition of the triblock copolymer into the DMPC: Tritonmore » X-100 bilayer increases the complexity (broadens) the lipid phase transition, further compresses the bilayer, and continues to expand the proximal hydrophilic layer thickness. The observed structural changes are temperature dependent with transmembrane polymer insertion achieved at 37 °C leading to a compressed membrane thickness of 39.2 ± 0.2 Å and proximal gap of 45.2 ± 0.2 Å. Temperature driven exclusion of the polymer at 15 °C causes partitioning of the polymer into the proximal space generating a large hydrogel cushion 162 ± 16 Å thick. An intermediate gap width (10 – 27 Å) is achieved at room temperature (22 – 25 °C). The temperature-driven changes in the proximal hydrophilic gap dimensions are shown to be reversible but thermal history causes variation in magnitude. Temperature-driven changes in polymer association with a supported lipid bilayer offer a facile means to reversibly control both the membrane characteristics as well as the separation between membrane and solid substrate.« less

Reversible Lifting of Surface Supported Lipid Bilayers with a Membrane-Spanning Nonionic Triblock Copolymer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayden, Steven C.; Junghans, Ann; Majewski, Jaroslaw

Neutron reflectometry was used to monitor structural variations in surface supported DMPC bilayers induced by the addition of Triton X-100, a surfactant commonly used to aid solubilization of membrane proteins, and the co-addition of a membrane spanning non-ionic amphiphilic triblock copolymer, (PEO 117-PPO 47-PE O117, Pluronic F98). Surfactant addition causes slight compression of the bilayer thickness and the creation of a distinct EO layer that increases the hydrophilic layer proximal to the supporting substrate (i.e., a water and EO gap between the lipid bilayer and quartz) to 6.8 ± 0.4 Å. Addition of the triblock copolymer into the DMPC: Tritonmore » X-100 bilayer increases the complexity (broadens) the lipid phase transition, further compresses the bilayer, and continues to expand the proximal hydrophilic layer thickness. The observed structural changes are temperature dependent with transmembrane polymer insertion achieved at 37 °C leading to a compressed membrane thickness of 39.2 ± 0.2 Å and proximal gap of 45.2 ± 0.2 Å. Temperature driven exclusion of the polymer at 15 °C causes partitioning of the polymer into the proximal space generating a large hydrogel cushion 162 ± 16 Å thick. An intermediate gap width (10 – 27 Å) is achieved at room temperature (22 – 25 °C). The temperature-driven changes in the proximal hydrophilic gap dimensions are shown to be reversible but thermal history causes variation in magnitude. Temperature-driven changes in polymer association with a supported lipid bilayer offer a facile means to reversibly control both the membrane characteristics as well as the separation between membrane and solid substrate.« less

Influence of ester-modified lipids on bilayer structure.

PubMed

Villanueva, Diana Y; Lim, Joseph B; Klauda, Jeffery B

2013-11-19

Lipid membranes function as barriers for cells to prevent unwanted chemicals from entering the cell and wanted chemicals from leaving. Because of their hydrophobic interior, membranes do not allow water to penetrate beyond the headgroup region. We performed molecular simulations to examine the effects of ester-modified lipids, which contain ester groups along their hydrocarbon chains, on bilayer structure. We chose two lipids from those presented in Menger et al. [J. Am. Chem. Soc. 2006, 128, 14034] with ester groups in (1) the upper half of the lipid chain (MEPC) and (2) the middle and end of the lipid chain (MGPC). MGPC (30%)/POPC bilayers formed stable water pores of diameter 5-7 Å, but MGPC (22%)/POPC and MEPC (30%)/POPC bilayers did not form these defects. These pores were similar to those formed during electroporation; i.e., the head groups lined the pore and allowed water and ions to transport across the bilayer. However, we found that lateral organization of the MGPC lipids into clusters, instead of an electric field or charge disparity as in electroporation, was essential for pore formation. On the basis of this, we propose an overall mechanism for pore formation. The similarities between the ester-modified lipids and byproducts of lipid peroxidation with multiple hydrophilic groups in the middle of the chain suggest that free radical reactions with unsaturated lipids and sterols result in fundamental changes that may be similar to what is seen in bilayers with ester-modified lipids.

Bi-layer channel structure-based oxide thin-film transistors consisting of ZnO and Al-doped ZnO with different Al compositions and stacking sequences

NASA Astrophysics Data System (ADS)

Cho, Sung Woon; Yun, Myeong Gu; Ahn, Cheol Hyoun; Kim, So Hee; Cho, Hyung Koun

2015-03-01

Zinc oxide (ZnO)-based bi-layers, consisting of ZnO and Al-doped ZnO (AZO) layers grown by atomic layer deposition, were utilized as the channels of oxide thin-film transistors (TFTs). Thin AZO layers (5 nm) with different Al compositions (5 and 14 at. %) were deposited on top of and beneath the ZnO layers in a bi-layer channel structure. All of the bi-layer channel TFTs that included the AZO layers showed enhanced stability (Δ V Th ≤ 3.2 V) under a positive bias stress compared to the ZnO single-layer channel TFT (Δ V Th = 4.0 V). However, the AZO/ZnO bi-layer channel TFTs with an AZO interlayer between the gate dielectric and the ZnO showed a degraded field effect mobility (0.3 cm2/V·s for 5 at. % and 1.8 cm2/V·s for 14 at. %) compared to the ZnO single-layer channel TFT (5.5 cm2/V·s) due to increased scattering caused by Al-related impurities near the gate dielectric/channel interface. In contrast, the ZnO/AZO bi-layer channel TFTs with an AZO layer on top of the ZnO layer exhibited an improved field effect mobility (7.8 cm2/V·s for 14 at. %) and better stability. [Figure not available: see fulltext.

Thermal transport characterization of stanene/silicene heterobilayer and stanene bilayer nanostructures

NASA Astrophysics Data System (ADS)

Noshin, Maliha; Intisar Khan, Asir; Subrina, Samia

2018-05-01

Recently, stanene and silicene based nanostructures with low thermal conductivity have incited noteworthy interest due to their prospect in thermoelectrics. Aiming at the possibility of extracting lower thermal conductivity, in this study, we have proposed and modeled stanene/silicene heterobilayer nanoribbons, a new heterostructure and subsequently characterized their thermal transport by using an equilibrium molecular dynamics simulation. In addition, the thermal transport in bilayer stanene is also studied and compared. We have computed the thermal conductivity of the stanene/silicene and bilayer stanene nanostructures to characterize their thermal transport phenomena. The studied nanostructures show good thermal stability within the temperature range of 100-600 K. The room temperature thermal conductivities of pristine 10 nm × 3 nm stanene/silicene hetero-bilayer and stanene bilayer are estimated to be 3.63 ± 0.27 W m-1 K-1 and 1.31 ± 0.34 W m-1 K-1, respectively, which are smaller than that of silicene, graphene and some other 2D monolayers as well as heterobilayers such as stanene/graphene and silicene/graphene. In the temperature range of 100-600 K, the thermal conductivity of our studied bilayer nanoribbons decreases with an increase in the temperature. Furthermore, we have investigated the dependence of our estimated thermal conductivity on the size of the considered nanoribbons. The thermal conductivities of both the nanoribbons are found to increase with an increase in the width of the structure. The thermal conductivity shows a similar increasing trend with the increase in the ribbon length, as well. Our results suggest that, the low thermal conductivity of our studied bilayer structures can be further decreased by nanostructuring. The significantly low thermal conductivity of the stanene/silicene heterobilayer and stanene bilayer nanoribbons realized in our study would provide a good insight and encouragement into their appealing prospect in the thermoelectric applications.

Thermal transport characterization of stanene/silicene heterobilayer and stanene bilayer nanostructures.

PubMed

Noshin, Maliha; Khan, Asir Intisar; Subrina, Samia

2018-05-04

Recently, stanene and silicene based nanostructures with low thermal conductivity have incited noteworthy interest due to their prospect in thermoelectrics. Aiming at the possibility of extracting lower thermal conductivity, in this study, we have proposed and modeled stanene/silicene heterobilayer nanoribbons, a new heterostructure and subsequently characterized their thermal transport by using an equilibrium molecular dynamics simulation. In addition, the thermal transport in bilayer stanene is also studied and compared. We have computed the thermal conductivity of the stanene/silicene and bilayer stanene nanostructures to characterize their thermal transport phenomena. The studied nanostructures show good thermal stability within the temperature range of 100-600 K. The room temperature thermal conductivities of pristine 10 nm × 3 nm stanene/silicene hetero-bilayer and stanene bilayer are estimated to be 3.63 ± 0.27 W m -1 K -1 and 1.31 ± 0.34 W m -1 K -1 , respectively, which are smaller than that of silicene, graphene and some other 2D monolayers as well as heterobilayers such as stanene/graphene and silicene/graphene. In the temperature range of 100-600 K, the thermal conductivity of our studied bilayer nanoribbons decreases with an increase in the temperature. Furthermore, we have investigated the dependence of our estimated thermal conductivity on the size of the considered nanoribbons. The thermal conductivities of both the nanoribbons are found to increase with an increase in the width of the structure. The thermal conductivity shows a similar increasing trend with the increase in the ribbon length, as well. Our results suggest that, the low thermal conductivity of our studied bilayer structures can be further decreased by nanostructuring. The significantly low thermal conductivity of the stanene/silicene heterobilayer and stanene bilayer nanoribbons realized in our study would provide a good insight and encouragement into their appealing prospect in the thermoelectric applications.

The influence of interface on spin pumping effect in Ni{sub 80}Fe{sub 20} /Tb bilayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yue, Jinjin; Jiang, Sheng; Zhang, Dong

2016-05-15

Focusing on the interface effect of the Ni{sub 80}Fe{sub 20} (Py)/terbium (Tb) bilayer, the influence of interface on the magnetization dynamic damping is investigated systematically. Two series of Py (12 nm)/Tb (d nm) films with and without copper (Cu) (1 nm) interlayer are deposited on silicon (Si) substrates by DC magnetron sputtering at room temperature. From vibrating sample magnetometer (VSM) measurements, the saturation magnetization (M{sub s}) decreases with increasing Tb thickness in Py/Tb bilayer while the decrease of M{sub s} is suppressed efficiently by inserting a Cu layer with even 1 nm of thickness. From the frequency dependence of ferromagneticmore » resonance (FMR) linewidth, we can obtain the Gilbert damping coefficient (α), α is found to exhibit an extreme enhancement in comparison to the single Py layer and shows an increasing trend with increasing Tb thickness. By inserting the Cu layer, α decreases significantly. From theoretical fitting, the spin diffusion length (λ{sub SD}) and spin mixing conductance (g{sup ↑↓}) are determined. It shows that the interface structure influences the spin mixing conductance but not the spin diffusion length.« less

Molecular dynamics investigation of dynamical properties of phosphatidylethanolamine lipid bilayers

NASA Astrophysics Data System (ADS)

Pitman, Michael C.; Suits, Frank; Gawrisch, Klaus; Feller, Scott E.

2005-06-01

We describe the dynamic behavior of a 1-stearoyl-2-oleoyl-phosphatidylethanolamine (SOPE) bilayer from a 20ns molecular dynamics simulation. The dynamics of individual molecules are characterized in terms of H2 spin-lattice relaxation rates, nuclear overhauser enhancement spectroscopy (NOESY) cross-relaxation rates, and lateral diffusion coefficients. Additionally, we describe the dynamics of hydrogen bonding through an analysis of hydrogen bond lifetimes and the time evolution of clusters of hydrogen bonded lipids. The simulated trajectory is shown to be consistent with experimental measures of internal, intermolecular, and diffusive motion. Consistent with our analysis of SOPE structure in the companion paper, we see hydrogen bonding dominating the dynamics of the interface region. Comparison of H2 T1 relaxation rates for chain methylene segments in phosphatidylcholine and phosphatidylethanolamine bilayers indicates that slower motion resulting from hydrogen bonding extends at least three carbons into the hydrophobic core. NOESY cross-relaxation rates compare well with experimental values, indicating the observed hydrogen bonding dynamics are realistic. Calculated lateral diffusion rates (4±1×10-8cm2/s) are comparable, though somewhat lower than, those determined by pulsed field gradient NMR methods.

Assembly of RNA nanostructures on supported lipid bilayers

NASA Astrophysics Data System (ADS)

Dabkowska, Aleksandra P.; Michanek, Agnes; Jaeger, Luc; Rabe, Michael; Chworos, Arkadiusz; Höök, Fredrik; Nylander, Tommy; Sparr, Emma

2014-12-01

The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nano-structures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces.The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nano-structures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces. Electronic supplementary information (ESI) available: Table with sequences of tRNA units used in this study; schematic structures of the RNA polyhedron and its building blocks; gel electrophoresis characterization of the RNA polyhedron and squares; AFM characterization of RNA tectosquare; schematic structures of RNA-9 and RNA-10 and their association with lipid bilayers; QCM-D frequency and dissipation data (as function of time) for adsorption of RNA polyhedrons, RNA squares and RNA9-10 TIRF images of RNA with Gelstar after photobleaching with analysis; Correlation plot in change of shear viscosity for TS3 and TO3-4 models for the stoichiometry of TS; QCM-D dissipation data for the sequential experiment in Fig. 5a; QCM-D and for the assembly of building blocks at the bilayer scaffold at varying bulk concentrations; QCM-D of adsorption of TS3. See DOI: 10.1039/c4nr05968a

The Interaction of Melittin with Dimyristoyl Phosphatidylcholine-Dimyristoyl Phosphatidylserine Lipid Bilayer Membranes

DOE PAGES

Rai, Durgesh K.; Qian, Shuo; Heller, William T.

2016-08-13

We report that membrane-active peptides (MAPs), which interact directly with the lipid bilayer of a cell and include toxins and host defense peptides, display lipid composition-dependent activity. Phosphatidylserine (PS) lipids are anionic lipids that are found throughout the cellular membranes of most eukaryotic organisms where they serve as both a functional component and as a precursor to phosphatidylethanolamine lipids. The inner leaflet of the plasma membrane contains more PS than the outer one, and the asymmetry is actively maintained. Here, the impact of the MAP melittin on the structure of lipid bilayer vesicles made of a mixture of phosphatidylcholine andmore » phosphatidylserine was studied. Small-angle neutron scattering of the MAP associated with selectively deuterium-labeled lipid bilayer vesicles revealed how the thickness and lipid composition of phosphatidylserine-containing vesicles change in response to melittin. The peptide thickens the lipid bilayer for concentrations up to P/L = 1/500, but membrane thinning results when P/L = 1/200. The thickness transition is accompanied by a large change in the distribution of DMPS between the leaflets of the bilayer. The change in composition is driven by electrostatic interactions, while the change in bilayer thickness is driven by changes in the interaction of the peptide with the headgroup region of the lipid bilayer. Lastly, the results provide new information about lipid-specific interactions that take place in mixed composition lipid bilayer membranes.« less

The Interaction of Melittin with Dimyristoyl Phosphatidylcholine-Dimyristoyl Phosphatidylserine Lipid Bilayer Membranes.

PubMed

Rai, Durgesh K; Qian, Shuo; Heller, William T

2016-11-01

Membrane-active peptides (MAPs), which interact directly with the lipid bilayer of a cell and include toxins and host defense peptides, display lipid composition-dependent activity. Phosphatidylserine (PS) lipids are anionic lipids that are found throughout the cellular membranes of most eukaryotic organisms where they serve as both a functional component and as a precursor to phosphatidylethanolamine lipids. The inner leaflet of the plasma membrane contains more PS than the outer one, and the asymmetry is actively maintained. Here, the impact of the MAP melittin on the structure of lipid bilayer vesicles made of a mixture of phosphatidylcholine and phosphatidylserine was studied. Small-angle neutron scattering of the MAP associated with selectively deuterium-labeled lipid bilayer vesicles revealed how the thickness and lipid composition of phosphatidylserine-containing vesicles change in response to melittin. The peptide thickens the lipid bilayer for concentrations up to P/L=1/500, but membrane thinning results when P/L=1/200. The thickness transition is accompanied by a large change in the distribution of DMPS between the leaflets of the bilayer. The change in composition is driven by electrostatic interactions, while the change in bilayer thickness is driven by changes in the interaction of the peptide with the headgroup region of the lipid bilayer. The results provide new information about lipid-specific interactions that take place in mixed composition lipid bilayer membranes. Copyright © 2016 Elsevier B.V. All rights reserved.

The use of virtual ground to control transmembrane voltages and measure bilayer currents in serial arrays of droplet interface bilayers

NASA Astrophysics Data System (ADS)

Sarles, Stephen A.

2013-09-01

The droplet interface bilayer (DIB) is a simple technique for constructing a stable lipid bilayer at the interface of two lipid-encased water droplets submerged in oil. Networks of DIBs formed by connecting more than two droplets constitute a new form of modular biomolecular smart material, where the transduction properties of a single lipid bilayer can affect the actions performed at other interface bilayers in the network via diffusion through the aqueous environments of shared droplet connections. The passive electrical properties of a lipid bilayer and the arrangement of droplets that determine the paths for transport in the network require specific electrical control to stimulate and interrogate each bilayer. Here, we explore the use of virtual ground for electrodes inserted into specific droplets in the network and employ a multichannel patch clamp amplifier to characterize bilayer formation and ion-channel activity in a serial DIB array. Analysis of serial connections of DIBs is discussed to understand how assigning electrode connections to the measurement device can be used to measure activity across all lipid membranes within a network. Serial arrays of DIBs are assembled using the regulated attachment method within a multi-compartment flexible substrate, and wire-type electrodes inserted into each droplet compartment of the substrate enable the application of voltage and measurement of current in each droplet in the array.

Indole Localization in an Explicit Bilayer Revealed via Molecular Dynamics

NASA Astrophysics Data System (ADS)

Norman, Kristen

2005-11-01

It is well known that the amino-acid tryptophan is particularly stable in the interfacial region of biological membranes, and this preference is a property of the tryptophan side-chain. Analogues of this side-chain, such as indole, strongly localize in the interfacial region, especially near the glycerol moiety of the lipids in the bilayer. Using molecular dynamics calculations, we determine the potential of mean force (PMF) for indoles in the bilayer. We compare the calculated PMF for indole with that of benzene to show that exclusion from the center of the lipid bilayer does not occur in all aromatics, but is strong in indoles. We find three minima in the PMF. Indole is most stabilized near the glycerol moiety. A weaker binding location is found near the choline groups of the lipid molecules. An even weaker binding side is found near the center of the lipid hydrocarbon core. Comparisions between uncharged, weakly charged, and highly charged indoles demonstrate that the exclusion is caused by the charge distribution on the indole rather than the ``lipo-phobic'' effect. High temperature simulations are used to determine the relative contribution of enthalpy and entropy to indole localization. The orientation of indole is found to be largely charge independent and is a strong function of depth within the bilayer. We find good agreement between simulated SCD order parameters for indole and experimentally determined order parameters.

Development of an automation technique for the establishment of functional lipid bilayer arrays

NASA Astrophysics Data System (ADS)

Hansen, J. S.; Perry, M.; Vogel, J.; Vissing, T.; Hansen, C. R.; Geschke, O.; Emnéus, J.; Nielsen, C. H.

2009-02-01

In the present work, a technique for establishing multiple black lipid membranes (BLMs) in arrays of micro structured ethylene tetrafluoroethylene (ETFE) films, and supported by a micro porous material was developed. Rectangular 8 × 8 arrays with apertures having diameters of 301 ± 5 µm were fabricated in ETFE Teflon film by laser ablation using a carbon dioxide laser. Multiple lipid membranes could be formed across the micro structured 8 × 8 array ETFE partitions. Success rates for the establishment of cellulose-supported BLMs across the multiple aperture arrays were above 95%. However, the time course of the membrane thinning process was found to vary considerably between multiple aperture bilayer experiments. An airbrush partition pretreatment technique was developed to increase the reproducibility of the multiple lipid bilayers formation during the time course from the establishment of the lipid membranes to the formation of bilayers. The results showed that multiple lipid bilayers could be reproducible formed across the airbrush-pretreated 8 × 8 rectangular arrays. The ionophoric peptide valinomycin was incorporated into established membrane arrays, resulting in ionic currents that could be effectively blocked by tetraethylammonium. This shows that functional bimolecular lipid membranes were established, and furthermore outlines that the established lipid membrane arrays could host functional membrane-spanning molecules.

Direct Imaging of Individual Intrinsic Hydration Layers on Lipid Bilayers at Ångstrom Resolution

PubMed Central

Fukuma, Takeshi; Higgins, Michael J.; Jarvis, Suzanne P.

2007-01-01

The interactions between water and biological molecules have the potential to influence the structure, dynamics, and function of biological systems, hence the importance of revealing the nature of these interactions in relation to the local biochemical environment. We have investigated the structuring of water at the interface of supported dipalmitoylphosphatidylcholine bilayers in the gel phase in phosphate buffer solution using frequency modulation atomic force microscopy (FM-AFM). We present experimental results supporting the existence of intrinsic (i.e., surface-induced) hydration layers adjacent to the bilayer. The force versus distance curves measured between the bilayer and the AFM tip show oscillatory force profiles with a peak spacing of 0.28 nm, indicative of the existence of up to two hydration layers next to the membrane surface. These oscillatory force profiles reveal the molecular-scale origin of the hydration force that has been observed between two apposing lipid bilayers. Furthermore, FM-AFM imaging at the water/lipid interface visualizes individual hydration layers in three dimensions, with molecular-scale corrugations corresponding to the lipid headgroups. The results demonstrate that the intrinsic hydration layers are stable enough to present multiple energy barriers to approaching nanoscale objects, such as proteins and solvated ions, and are expected to affect membrane permeability and transport. PMID:17325013

Bilayer synergetic coupling double negative acoustic metasurface and cloak.

PubMed

Ma, Fuyin; Huang, Meng; Xu, Yicai; Wu, Jiu Hui

2018-04-12

In this paper, we propose a bilayer plate-type lightweight double negative metasurface based on a new synergetic coupling design concept, by which the perfect absorption, double negative bands, free manipulation of phase shifts with a 2π span and acoustic cloak can be successively realized. Firstly, the synergetic behavior between resonant and anti-resonant plates is presented to construct a bilayer unit in which each component respectively provides a pre-defined function in realizing the perfect absorption. Based on this bilayer structure, a double negative band with simultaneously negative effective mass density and bulk modulus is obtained, which, as a metasurface, can obtain continuous phase shifts almost completely covering a 2π range, thus facilitating the design of a three-dimensional (3D) acoustic cloak. In addition, based on this strong sound absorption concept, a two-dimensional (2D) omnidirectional broadband acoustical dark skin, covering between 800 to 6000 Hz, is also demonstrated through the proposed bilayer plate-type structure form. The proposed design concepts and metasurfaces have widespread potential application values in strong sound attenuation, filtering, superlens, imaging, cloak, and extraordinary wave steering, in which the attributes of strong absorption, double negative parameters or continuous phase shifts with full 2π span are required to realize the expected extraordinary physical features.

Impact of cholesterol on voids in phospholipid membranes

NASA Astrophysics Data System (ADS)

Falck, Emma; Patra, Michael; Karttunen, Mikko; Hyvönen, Marja T.; Vattulainen, Ilpo

2004-12-01

Free volume pockets or voids are important to many biological processes in cell membranes. Free volume fluctuations are a prerequisite for diffusion of lipids and other macromolecules in lipid bilayers. Permeation of small solutes across a membrane, as well as diffusion of solutes in the membrane interior are further examples of phenomena where voids and their properties play a central role. Cholesterol has been suggested to change the structure and function of membranes by altering their free volume properties. We study the effect of cholesterol on the properties of voids in dipalmitoylphosphatidylcholine (DPPC) bilayers by means of atomistic molecular dynamics simulations. We find that an increasing cholesterol concentration reduces the total amount of free volume in a bilayer. The effect of cholesterol on individual voids is most prominent in the region where the steroid ring structures of cholesterol molecules are located. Here a growing cholesterol content reduces the number of voids, completely removing voids of the size of a cholesterol molecule. The voids also become more elongated. The broad orientational distribution of voids observed in pure DPPC is, with a 30% molar concentration of cholesterol, replaced by a distribution where orientation along the bilayer normal is favored. Our results suggest that instead of being uniformly distributed to the whole bilayer, these effects are localized to the close vicinity of cholesterol molecules.

Bifurcation of self-folded polygonal bilayers

NASA Astrophysics Data System (ADS)

Abdullah, Arif M.; Braun, Paul V.; Hsia, K. Jimmy

2017-09-01

Motivated by the self-assembly of natural systems, researchers have investigated the stimulus-responsive curving of thin-shell structures, which is also known as self-folding. Self-folding strategies not only offer possibilities to realize complicated shapes but also promise actuation at small length scales. Biaxial mismatch strain driven self-folding bilayers demonstrate bifurcation of equilibrium shapes (from quasi-axisymmetric doubly curved to approximately singly curved) during their stimulus-responsive morphing behavior. Being a structurally instable, bifurcation could be used to tune the self-folding behavior, and hence, a detailed understanding of this phenomenon is appealing from both fundamental and practical perspectives. In this work, we investigated the bifurcation behavior of self-folding bilayer polygons. For the mechanistic understanding, we developed finite element models of planar bilayers (consisting of a stimulus-responsive and a passive layer of material) that transform into 3D curved configurations. Our experiments with cross-linked Polydimethylsiloxane samples that change shapes in organic solvents confirmed our model predictions. Finally, we explored a design scheme to generate gripper-like architectures by avoiding the bifurcation of stimulus-responsive bilayers. Our research contributes to the broad field of self-assembly as the findings could motivate functional devices across multiple disciplines such as robotics, artificial muscles, therapeutic cargos, and reconfigurable biomedical devices.

Evaluation of the performance characteristics of bilayer tablets: Part II. Impact of environmental conditions on the strength of bilayer tablets.

PubMed

Kottala, Niranjan; Abebe, Admassu; Sprockel, Omar; Bergum, James; Nikfar, Faranak; Cuitiño, Alberto M

2012-12-01

Ambient air humidity and temperature are known to influence the mechanical strength of tablets. The objective of this work is to understand the influence of processing parameters and environmental conditions (humidity and temperature) on the strength of bilayer tablets. As part of this study, bilayer tablets were compressed with different layer ratios, dwell times, layer sequences, material properties (plastic and brittle), first and second layer forces, and lubricant concentrations. Compressed tablets were stored in stability chambers controlled at predetermined conditions (40C/45%RH, 40C/75%RH) for 1, 3, and 5 days. The axial strength of the stored tablets was measured and a statistical model was developed to determine the effects of the aforementioned factors on the strength of bilayer tablets. As part of this endeavor, a full 3 × 2(4) factorial design was executed. Responses of the experiments were analyzed using PROC GLM of SAS (SAS Institute Inc, Cary, North Carolina, USA). A model was fit using all the responses to determine the significant interactions (p < 0.05). Results of this study indicated that storage conditions and storage time have significant impact on the strength of bilayer tablets. For Avicel-lactose and lactose-Avicel tablets, tablet strength decreased with the increasing humidity and storage time. But for lactose-lactose tablets, due to the formation of solid bridges upon storage, an increase in tablet strength was observed. Significant interactions were observed between processing parameters and storage conditions on the strength of bilayer tablets.

Mechanical property characterization of bilayered tablets using nondestructive air-coupled acoustics.

PubMed

Akseli, Ilgaz; Dey, Dipankar; Cetinkaya, Cetin

2010-03-01

A noncontact/nondestructive air-coupled acoustic technique to be potentially used in mechanical property determination of bilayer tablets is presented. In the reported experiments, a bilayer tablet is vibrated via an acoustic field of an air-coupled transducer in a frequency range sufficiently high to excite several vibrational modes (harmonics) of the tablet. The tablet vibrational transient responses at a number of measurement points on the tablet are acquired by a laser vibrometer in a noncontact manner. An iterative computational procedure based on the finite element method is utilized to extract the Young's modulus, the Poisson's ratio, and the mass density values of each layer material of a bilayer tablet from a subset of the measured resonance frequencies. For verification purposes, a contact ultrasonic technique based on the time-of-flight data of the longitudinal (pressure) and transverse (shear) acoustic waves in each layer of a bilayer tablet is also utilized. The extracted mechanical properties from the air-coupled acoustic data agree well with those determined from the contact ultrasonic measurements. The mechanical properties of solid oral dosage forms have been shown to impact its mechanical integrity, disintegration profile and the release rate of the drug in the digestive tract, thus potentially affecting its therapeutic response. The presented nondestructive technique provides greater insight into the mechanical properties of the bilayer tablets and has the potential to identify quality and performance problems related to the mechanical properties of the bilayer tablets early on the production process and, consequently, reduce associated cost and material waste.

Exciton dynamics and annihilation in WS2 2D semiconductors.

PubMed

Yuan, Long; Huang, Libai

2015-04-28

We systematically investigate the exciton dynamics in monolayered, bilayered, and trilayered WS2 two-dimensional (2D) crystals by time-resolved photoluminescence (TRPL) spectroscopy. The exciton lifetime when free of exciton annihilation was determined to be 806 ± 37 ps, 401 ± 25 ps, and 332 ± 19 ps for WS2 monolayer, bilayer, and trilayer, respectively. By measuring the fluorescence quantum yields, we also establish the radiative and nonradiative lifetimes of the direct and indirect excitons. The exciton decay in monolayered WS2 exhibits a strong excitation density-dependence, which can be described using an exciton-exciton annihilation (two-particle Auger recombination) model. The exciton-exciton annihilation rate for monolayered, bilayered, and trilayered WS2 was determined to be 0.41 ± 0.02, (6.00 ± 1.09) × 10(-3) and (1.88 ± 0.47) × 10(-3) cm(2) s(-1), respectively. Notably, the exciton-exciton annihilation rate is two orders of magnitude faster in the monolayer than in the bilayer and trilayer. We attribute the much slower exciton-exciton annihilation rate in the bilayer and trilayer to reduced many-body interaction and phonon-assisted exciton-exciton annihilation of indirect excitons.

Membrane and Protein Interactions of the Pleckstrin Homology Domain Superfamily

PubMed Central

Lenoir, Marc; Kufareva, Irina; Abagyan, Ruben; Overduin, Michael

2015-01-01

The human genome encodes about 285 proteins that contain at least one annotated pleckstrin homology (PH) domain. As the first phosphoinositide binding module domain to be discovered, the PH domain recruits diverse protein architectures to cellular membranes. PH domains constitute one of the largest protein superfamilies, and have diverged to regulate many different signaling proteins and modules such as Dbl homology (DH) and Tec homology (TH) domains. The ligands of approximately 70 PH domains have been validated by binding assays and complexed structures, allowing meaningful extrapolation across the entire superfamily. Here the Membrane Optimal Docking Area (MODA) program is used at a genome-wide level to identify all membrane docking PH structures and map their lipid-binding determinants. In addition to the linear sequence motifs which are employed for phosphoinositide recognition, the three dimensional structural features that allow peripheral membrane domains to approach and insert into the bilayer are pinpointed and can be predicted ab initio. The analysis shows that conserved structural surfaces distinguish which PH domains associate with membrane from those that do not. Moreover, the results indicate that lipid-binding PH domains can be classified into different functional subgroups based on the type of membrane insertion elements they project towards the bilayer. PMID:26512702

Tunable mesoporous bilayer photonic resins with chiral nematic structures and actuator properties.

PubMed

Khan, Mostofa K; Hamad, Wadood Y; Maclachlan, Mark J

2014-04-16

Chiral nematic structures with different helical pitch from layer to layer are embedded into phenol-formaldehyde bilayer resin composite films using cellulose nanocrystals (CNCs) as templates. Selective removal of CNCs results in mesoporous resins with different pore size and helical pitch between the layers. Consequently, these materials exhibit photonic properties by selectively reflecting lights of two different wavelengths and concomitant actuation properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal Response Analysis of Phospholipid Bilayers Using Ellipsometric Techniques.

PubMed

González-Henríquez, Carmen M; Villegas-Opazo, Vanessa A; Sagredo-Oyarce, Dallits H; Sarabia-Vallejos, Mauricio A; Terraza, Claudio A

2017-08-18

Biomimetic planar artificial membranes have been widely studied due to their multiple applications in several research fields. Their humectation and thermal response are crucial for reaching stability; these characteristics are related to the molecular organization inside the bilayer, which is affected by the aliphatic chain length, saturations, and molecule polarity, among others. Bilayer stability becomes a fundamental factor when technological devices are developed-like biosensors-based on those systems. Thermal studies were performed for different types of phosphatidylcholine (PC) molecules: two pure PC bilayers and four binary PC mixtures. These analyses were carried out through the detection of slight changes in their optical and structural parameters via Ellipsometry and Surface Plasmon Resonance (SPR) techniques. Phospholipid bilayers were prepared by Langmuir-Blodgett technique and deposited over a hydrophilic silicon wafer. Their molecular inclination degree, mobility, and stability of the different phases were detected and analyzed through bilayer thickness changes and their optical phase-amplitude response. Results show that certain binary lipid mixtures-with differences in its aliphatic chain length-present a co-existence of two thermal responses due to non-ideal mixing.

Neutron Reflectivity as a Tool for Physics-Based Studies of Model Bacterial Membranes.

PubMed

Barker, Robert D; McKinley, Laura E; Titmuss, Simon

2016-01-01

The principles of neutron reflectivity and its application as a tool to provide structural information at the (sub-) molecular unit length scale from models for bacterial membranes are described. The model membranes can take the form of a monolayer for a single leaflet spread at the air/water interface, or bilayers of increasing complexity at the solid/liquid interface. Solid-supported bilayers constrain the bilayer to 2D but can be used to characterize interactions with antimicrobial peptides and benchmark high throughput lab-based techniques. Floating bilayers allow for membrane fluctuations, making the phase behaviour more representative of native membranes. Bilayers of varying levels of compositional accuracy can now be constructed, facilitating studies with aims that range from characterizing the fundamental physical interactions, through to the characterization of accurate mimetics for the inner and outer membranes of Gram-negative bacteria. Studies of the interactions of antimicrobial peptides with monolayer and bilayer models for the inner and outer membranes have revealed information about the molecular control of the outer membrane permeability, and the mode of interaction of antimicrobials with both inner and outer membranes.

Effect of vacuum thermal annealing on a molybdenum bilayer back contact deposited by radio-frequency magnetron sputtering for chalcogenide- and kesterite-based solar cells

NASA Astrophysics Data System (ADS)

Liu, Xiaolei; Cui, Hongtao; Hao, Xiaojing; Huang, Shujuan; Conibeer, Gavin

2017-12-01

Molybdenum (Mo) thin films are still a dominant choice for the back contact layer of Cu(In,Ga)Se2 (CIGS) and Cu2ZnSnS4 (CZTS) solar cells. This paper presents a review of Mo back contacts for CIGS and CZTS solar cells, including the requirements for a good back contact, the reason for the choice of Mo, and post-treatment. Additionally, a Mo bilayer back contact was fabricated by varying the argon (Ar) pressure during sputtering to provide both low resistivity and good adhesion to the soda-lime glass substrate. The effects of vacuum thermal annealing on the electrical, morphological and structural properties of the Mo bilayer were also investigated. Vacuum thermal annealing was seen to densify the Mo bilayer, reduce the sheet resistance, and improve the bilayer's adhesion to the soda-lime glass. The Mo bilayer back contact with a low sheet resistance of 0.132 Ω/□ and strong adhesion was made for chalcogenide- and kesterite-based solar cells.

The electronic transport properties of defected bilayer sliding armchair graphene nanoribbons

NASA Astrophysics Data System (ADS)

Mohammadi, Amin; Haji-Nasiri, Saeed

2018-04-01

By applying non-equilibrium Green's functions (NEGF) in combination with tight-binding (TB) model, we investigate and compare the electronic transport properties of perfect and defected bilayer armchair graphene nanoribbons (BAGNRs) under finite bias. Two typical defects which are placed in the middle of top layer (i.e. single vacancy (SV) and stone wale (SW) defects) are examined. The results reveal that in both perfect and defected bilayers, the maximum current refers to β-AB, AA and α-AB stacking orders, respectively, since the intermolecular interactions are stronger in them. Moreover it is observed that a SV decreases the current in all stacking orders, but the effects of a SW defect is nearly unpredictable. Besides, we introduced a sequential switching behavior and the effects of defects on the switching performance is studied as well. We found that a SW defect can significantly improve the switching behavior of a bilayer system. Transmission spectrum, band structure, molecular energy spectrum and molecular projected self-consistent Hamiltonian (MPSH) are analyzed subsequently to understand the electronic transport properties of these bilayer devices which can be used in developing nano-scale bilayer systems.

Synthesis, structure, and characterization of two Zn(II) complex containing two-dimensional bilayer structure

NASA Astrophysics Data System (ADS)

Zhang, Meili; Ren, Yixia; Chen, Xiaoli

2014-10-01

Two new Zn(II) complexes, [Zn2(L)(H2O)3]ṡH2O (1) and [Zn3(HL)2(bpp)2(Hbpp)2]ṡ10H2Oṡ2ClO4 (2) (H4L = cis,cis,cis,cis-1,2,3,4-cyclopentanetracarboxylic acid, bpp = 1,3-bis(4-pyridyl)propane), have been synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction techniques. The structure indicates that the complex 1 crystallizes in triclinic, space group Pī, in which, the four carboxylate groups of L ligand adopt μ2-η1:η0, μ2-η1:η1, μ1-η1:η1 coordination modes, respectively, bridging Zn(II) atoms to generate a (4,6)-connected 2D bilayer network. The structure indicates that the complex 2 crystallizes in monoclinic, space group C2/c, in which, three deprotonated carboxylate groups of L ligand adopt uniform μ1-η1:η0 coordination mode linking Zn(II) atoms to form a 1D polymeric ribbon, the bpp ligands further extend such ribbon giving rised to a (3,4)-connected 2D bilayer network. The most striking feature of 1 and 2 is that both of bilayer networks contain 1D solvent channel, where water molecules are located. In additional, luminescent properties of two complexes have also been studied.

Subterahertz Longitudinal Phonon Modes Propagating in a Lipid Bilayer Immersed in an Aqueous Medium

NASA Astrophysics Data System (ADS)

Zakhvataev, V. E.

2018-04-01

The properties of subterahertz longitudinal acoustic phonon modes in the hydrophobic region of a lipid bilayer immersed in a compressible viscous aqueous medium are investigated theoretically. An approximate expression is obtained for the Mandelstam-Brillouin components of the dynamic structure factor of a bilayer. The analysis is based on a generalized hydrodynamic model of the "two-dimensional lipid bilayer + three-dimensional fluid medium" system, as well as on known sharp estimates for the frequencies and lifetimes of long-wavelength longitudinal acoustic phonons in a free hydrated lipid bilayer and in water, obtained from inelastic X-ray scattering experiments and molecular dynamics simulations. It is shown that, for characteristic values of the parameters of the membrane system, subterahertz longitudinal phonon-like excitations in the hydrophobic part of the bilayer are underdamped. In this case, the contribution of the viscous flow of the aqueous medium to the damping of a longitudinal membrane mode is small compared with the contribution of the lipid bilayer. Quantitative estimates of the damping ratio agree well with the experimental results for the vibration mode of the enzyme lysozyme in aqueous solution [1]. It is also shown that a coupling between longitudinal phonon modes of the bilayer and relaxation processes in its fluid environment gives rise to an additional peak in the scattering spectrum, which corresponds to a non-propagating mode.

Coexistence of a two-states organization for a cell-penetrating peptide in lipid bilayer.

PubMed

Plénat, Thomas; Boichot, Sylvie; Dosset, Patrice; Milhiet, Pierre-Emmanuel; Le Grimellec, Christian

2005-12-01

Primary amphipathic cell-penetrating peptides transport cargoes across cell membranes with high efficiency and low lytic activity. These primary amphipathic peptides were previously shown to form aggregates or supramolecular structures in mixed lipid-peptide monolayers, but their behavior in lipid bilayers remains to be characterized. Using atomic force microscopy, we have examined the interactions of P(alpha), a primary amphipathic cell-penetrating peptide which remains alpha-helical whatever the environment, with dipalmitoylphosphatidylcholine (DPPC) bilayers. Addition of P(alpha) at concentrations up to 5 mol % markedly modified the supported bilayers topography. Long and thin filaments lying flat at the membrane surface coexisted with deeply embedded peptides which induced a local thinning of the bilayer. On the other hand, addition of P(alpha) only exerted very limited effects on the corresponding liposome's bilayer physical state, as estimated from differential scanning calorimetry and diphenylhexatriene fluorescence anisotropy experiments. The use of a gel-fluid phase separated supported bilayers made of a dioleoylphosphatidylcholine/dipalmitoylphosphatidylcholine mixture confirmed both the existence of long filaments, which at low peptide concentration were preferentially localized in the fluid phase domains and the membrane disorganizing effects of 5 mol % P(alpha). The simultaneous two-states organization of P(alpha), at the membrane surface and deeply embedded in the bilayer, may be involved in the transmembrane carrier function of this primary amphipathic peptide.

Salt-induced effects on natural and inverse DPPC lipid membranes: Molecular dynamics simulation.

PubMed

Rezaei Sani, Seyed Mojtaba; Akhavan, Mojdeh; Jalili, Seifollah

2018-08-01

Molecular dynamics (MD) simulations of a dipalmitoylphosphatidylcholine (DPPC) bilayer and its neutral inverse-phosphocholine equivalent (DPCPe) were performed to find salt-induced effects on their surface structure and the nature of ion-lipid interactions. We found that the area per lipid is not considerably affected by the inversion, but the deuterium order parameter of carbon atoms in the region of carbonyl carbons changes dramatically. MD simulations indicate that Ca 2+ ions can bind to the surface of both DPPC and DPCPe membranes, but K + ions do not bind to them. In the case of Na + , however, the ions can bind to natural lipids but not to the inverse ones. Also, our results demonstrate that the hydration level of CPe bilayers is substantially lower than PC bilayers and the averaged orientation of water dipoles in the region of CPe headgroups is effectively inverted compared to PC lipids. This might be important in the interaction of the bilayer with its biological environment. Furthermore, it was found for the CPe bilayers that the enhanced peaks of the electrostatic potential profiles shift further away from the bilayer center relative to those of PC bilayers. This behavior makes the penetration of cations into the bilayer more difficult and possibly explains the experimentally observed enhanced release rates of anionic compounds in the CPe membrane. Copyright © 2018 Elsevier B.V. All rights reserved.

3-Methyl-7-(2-thienyl)pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione: pi-stacked bilayers built from N-H...O, C-H...O and C-H...pi hydrogen bonds.

PubMed

Trilleras, Jorge; Quiroga, Jairo; Cobo, Justo; Glidewell, Christopher

2009-06-01

In the title compound, C(12)H(9)N(3)O(2)S, the thienyl substituent is disordered over two sets of sites with occupancies of 0.749 (3) and 0.251 (3). A combination of N-H...O, C-H...O and C-H...pi hydrogen bonds links the molecules into bilayers and these bilayers are themselves linked into a continuous structure by pi-pi stacking interactions.

Optical Pulling and Pushing Forces in Bilayer P T -Symmetric Structures

NASA Astrophysics Data System (ADS)

Alaee, Rasoul; Christensen, Johan; Kadic, Muamer

2018-01-01

We investigate the optical force exerted on a parity-time-symmetric bilayer made of balanced gain and loss. We show that an asymmetric optical pulling or pushing force can be exerted on this system depending on the direction of impinging light. The optical pulling or pushing force has a direct physical link to the optical characteristics embedded in the non-Hermitian bilayer. Furthermore, we suggest taking advantage of the optically generated asymmetric force to launch vibrations of an arbitrary shape, which is useful for the contactless probing of mechanical deformations.

Shallow boomerang-shaped influenza hemagglutinin G13A mutant structure promotes leaky membrane fusion.

PubMed

Lai, Alex L; Tamm, Lukas K

2010-11-26

Our previous studies showed that an angled boomerang-shaped structure of the influenza hemagglutinin (HA) fusion domain is critical for virus entry into host cells by membrane fusion. Because the acute angle of ∼105° of the wild-type fusion domain promotes efficient non-leaky membrane fusion, we asked whether different angles would still support fusion and thus facilitate virus entry. Here, we show that the G13A fusion domain mutant produces a new leaky fusion phenotype. The mutant fusion domain structure was solved by NMR spectroscopy in a lipid environment at fusion pH. The mutant adopted a boomerang structure similar to that of wild type but with a shallower kink angle of ∼150°. G13A perturbed the structure of model membranes to a lesser degree than wild type but to a greater degree than non-fusogenic fusion domain mutants. The strength of G13A binding to lipid bilayers was also intermediate between that of wild type and non-fusogenic mutants. These membrane interactions provide a clear link between structure and function of influenza fusion domains: an acute angle is required to promote clean non-leaky fusion suitable for virus entry presumably by interaction of the fusion domain with the transmembrane domain deep in the lipid bilayer. A shallower angle perturbs the bilayer of the target membrane so that it becomes leaky and unable to form a clean fusion pore. Mutants with no fixed boomerang angle interacted with bilayers weakly and did not promote any fusion or membrane perturbation.

Shallow Boomerang-shaped Influenza Hemagglutinin G13A Mutant Structure Promotes Leaky Membrane Fusion*

PubMed Central

Lai, Alex L.; Tamm, Lukas K.

2010-01-01

Our previous studies showed that an angled boomerang-shaped structure of the influenza hemagglutinin (HA) fusion domain is critical for virus entry into host cells by membrane fusion. Because the acute angle of ∼105° of the wild-type fusion domain promotes efficient non-leaky membrane fusion, we asked whether different angles would still support fusion and thus facilitate virus entry. Here, we show that the G13A fusion domain mutant produces a new leaky fusion phenotype. The mutant fusion domain structure was solved by NMR spectroscopy in a lipid environment at fusion pH. The mutant adopted a boomerang structure similar to that of wild type but with a shallower kink angle of ∼150°. G13A perturbed the structure of model membranes to a lesser degree than wild type but to a greater degree than non-fusogenic fusion domain mutants. The strength of G13A binding to lipid bilayers was also intermediate between that of wild type and non-fusogenic mutants. These membrane interactions provide a clear link between structure and function of influenza fusion domains: an acute angle is required to promote clean non-leaky fusion suitable for virus entry presumably by interaction of the fusion domain with the transmembrane domain deep in the lipid bilayer. A shallower angle perturbs the bilayer of the target membrane so that it becomes leaky and unable to form a clean fusion pore. Mutants with no fixed boomerang angle interacted with bilayers weakly and did not promote any fusion or membrane perturbation. PMID:20826788

The three-dimensional structure of aquaporin-1

NASA Astrophysics Data System (ADS)

Walz, Thomas; Hirai, Teruhisa; Murata, Kazuyoshi; Heymann, J. Bernard; Mitsuoka, Kaoru; Fujiyoshi, Yoshinori; Smith, Barbara L.; Agre, Peter; Engel, Andreas

1997-06-01

The entry and exit of water from cells is a fundamental process of life. Recognition of the high water permeability of red blood cells led to the proposal that specialized water pores exist in the plasma membrane. Expression in Xenopus oocytes and functional studies of an erythrocyte integral membrane protein of relative molecular mass 28,000, identified it as the mercury-sensitive water channel, aquaporin-1 (AQP1). Many related proteins, all belonging to the major intrinsic protein (MIP) family, are found throughout nature. AQP1 is a homotetramer containing four independent aqueous channels. When reconstituted into lipid bilayers, the protein forms two-dimensional lattices with a unit cell containing two tetramers in opposite orientation. Here we present the three-dimensional structure of AQP1 determined at 6Å resolution by cryo-electron microscopy. Each AQP1 monomer has six tilted, bilayer-spanning α-helices which form a right-handed bundle surrounding a central density. These results, together with functional studies, provide a model that identifies the aqueous pore in the AQP1 molecule and indicates the organization of the tetrameric complex in the membrane.

Vapor deposition of water on graphitic surfaces: formation of amorphous ice, bilayer ice, ice I, and liquid water.

PubMed

Lupi, Laura; Kastelowitz, Noah; Molinero, Valeria

2014-11-14

Carbonaceous surfaces are a major source of atmospheric particles and could play an important role in the formation of ice. Here we investigate through molecular simulations the stability, metastability, and molecular pathways of deposition of amorphous ice, bilayer ice, and ice I from water vapor on graphitic and atomless Lennard-Jones surfaces as a function of temperature. We find that bilayer ice is the most stable ice polymorph for small cluster sizes, nevertheless it can grow metastable well above its region of thermodynamic stability. In agreement with experiments, the simulations predict that on increasing temperature the outcome of water deposition is amorphous ice, bilayer ice, ice I, and liquid water. The deposition nucleation of bilayer ice and ice I is preceded by the formation of small liquid clusters, which have two wetting states: bilayer pancake-like (wetting) at small cluster size and droplet-like (non-wetting) at larger cluster size. The wetting state of liquid clusters determines which ice polymorph is nucleated: bilayer ice nucleates from wetting bilayer liquid clusters and ice I from non-wetting liquid clusters. The maximum temperature for nucleation of bilayer ice on flat surfaces, T(B)(max) is given by the maximum temperature for which liquid water clusters reach the equilibrium melting line of bilayer ice as wetting bilayer clusters. Increasing water-surface attraction stabilizes the pancake-like wetting state of liquid clusters leading to larger T(B)(max) for the flat non-hydrogen bonding surfaces of this study. The findings of this study should be of relevance for the understanding of ice formation by deposition mode on carbonaceous atmospheric particles, including soot.

Nature of Interlayer Binding and Stacking of sp–sp 2 Hybridized Carbon Layers: A Quantum Monte Carlo Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shin, Hyeondeok; Kim, Jeongnim; Lee, Hoonkyung

α-graphyne is a two-dimensional sheet of sp-sp2 hybridized carbon atoms in a honeycomb lattice. While the geometrical structure is similar to that of graphene, the hybridized triple bonds give rise to electronic structure that is different from that of graphene. Similar to graphene, α-graphyne can be stacked in bilayers with two stable configurations, but the different stackings have very different electronic structures: one is predicted to have gapless parabolic bands and the other a tunable bandgap which is attractive for applications. In order to realize applications, it is crucial to understand which stacking is more stable. This is difficult tomore » model, as the stability is a result of weak interlayer van der Waals interactions which are not well captured by density functional theory (DFT). We have used quantum Monte Carlo simulations that accurately include van der Waals interactions to calculate the interlayer binding energy of bilayer graphyne and to determine its most stable stacking mode. Our results show that inter-layer bindings of sp- and sp2-bonded carbon networks are significantly underestimated in a Kohn-Sham DFT approach, even with an exchange-correlation potential corrected to include, in some approximation, van der Waals interactions. Finally, our quantum Monte Carlo calculations reveal that the interlayer binding energy difference between the two stacking modes is only 0.9(4) eV/atom. From this we conclude that the two stable stacking modes of bilayer α-graphyne are almost degenerate with each other, and both will occur with about the same probability at room temperature unless there is a synthesis path that prefers one stacking over the other.« less

Nature of Interlayer Binding and Stacking of sp–sp 2 Hybridized Carbon Layers: A Quantum Monte Carlo Study

DOE PAGES

Shin, Hyeondeok; Kim, Jeongnim; Lee, Hoonkyung; ...

2017-10-25

α-graphyne is a two-dimensional sheet of sp-sp2 hybridized carbon atoms in a honeycomb lattice. While the geometrical structure is similar to that of graphene, the hybridized triple bonds give rise to electronic structure that is different from that of graphene. Similar to graphene, α-graphyne can be stacked in bilayers with two stable configurations, but the different stackings have very different electronic structures: one is predicted to have gapless parabolic bands and the other a tunable bandgap which is attractive for applications. In order to realize applications, it is crucial to understand which stacking is more stable. This is difficult tomore » model, as the stability is a result of weak interlayer van der Waals interactions which are not well captured by density functional theory (DFT). We have used quantum Monte Carlo simulations that accurately include van der Waals interactions to calculate the interlayer binding energy of bilayer graphyne and to determine its most stable stacking mode. Our results show that inter-layer bindings of sp- and sp2-bonded carbon networks are significantly underestimated in a Kohn-Sham DFT approach, even with an exchange-correlation potential corrected to include, in some approximation, van der Waals interactions. Finally, our quantum Monte Carlo calculations reveal that the interlayer binding energy difference between the two stacking modes is only 0.9(4) eV/atom. From this we conclude that the two stable stacking modes of bilayer α-graphyne are almost degenerate with each other, and both will occur with about the same probability at room temperature unless there is a synthesis path that prefers one stacking over the other.« less

Phospholamban and its Phosphorylated Form Interact Differently with Lipid Bilayers: A 31P, 2H and 13C Solid-State NMR Spectroscopic Study

PubMed Central

Abu-Baker, Shadi; Lorigan, Gary A.

2008-01-01

Phospholamban (PLB) is a 52-amino acid integral membrane protein that helps to regulate the flow of Ca2+ ions in cardiac muscle cells. Recent structural studies on the PLB pentamer and the functionally active monomer (AFA-PLB) debate whether its cytoplasmic domain, in either the phosphorylated or dephosphorylated states, is α-helical in structure as well as whether it associates with the lipid head groups [Oxenoid, K. (2005) Proc Natl. Acad. Sci. USA 102, 10870–10875, Karim, C. B. (2004) Proc. Natl. Acad. Sci. USA 101, 14437–14442, Andronesi, C.A. (2005) J. Am. Chem. Soc. 127, 12965–12974, Li, J. (2003) Biochemistry 42, 10674–10682, Metcalfe, E. E. (2005) Biochemistry 44, 4386–4396, Clayton, J. C. (2005) Biochemistry 44, 17016–17026]. Comparing the secondary structure of the PLB pentamer and its phosphorylated form (P-PLB) as well as their interaction with the lipid bilayer is crucial in order to understand its regulatory function. Therefore, in this study, the full-length wild-type (WT)-PLB and P-PLB were incorporated into 1-palmitoyl-2-oleoyl-sn-glycero-phosphocholine (POPC) phospholipid bilayers and studied utilizing solid-state NMR spectroscopy. The analysis of the 2H and 31P solid-state NMR data of PLB and P-PLB in POPC multilamellar vesicles (MLVs) indicates that a direct interaction takes place between both proteins and the phospholipid head groups. However, the interaction of P-PLB with POPC bilayers was less significant when compared to PLB. Moreover, the secondary structure using 13C=O site-specific isotopically labeled Ala15-PLB and Ala15-P-PLB in POPC bilayers suggests that this residue, located in the cytoplasmic domain, is a part of an α-helical structure for both PLB and P-PLB. PMID:17073452

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lupi, Laura; Kastelowitz, Noah; Molinero, Valeria, E-mail: Valeria.Molinero@utah.edu

Carbonaceous surfaces are a major source of atmospheric particles and could play an important role in the formation of ice. Here we investigate through molecular simulations the stability, metastability, and molecular pathways of deposition of amorphous ice, bilayer ice, and ice I from water vapor on graphitic and atomless Lennard-Jones surfaces as a function of temperature. We find that bilayer ice is the most stable ice polymorph for small cluster sizes, nevertheless it can grow metastable well above its region of thermodynamic stability. In agreement with experiments, the simulations predict that on increasing temperature the outcome of water deposition ismore » amorphous ice, bilayer ice, ice I, and liquid water. The deposition nucleation of bilayer ice and ice I is preceded by the formation of small liquid clusters, which have two wetting states: bilayer pancake-like (wetting) at small cluster size and droplet-like (non-wetting) at larger cluster size. The wetting state of liquid clusters determines which ice polymorph is nucleated: bilayer ice nucleates from wetting bilayer liquid clusters and ice I from non-wetting liquid clusters. The maximum temperature for nucleation of bilayer ice on flat surfaces, T{sub B}{sup max} is given by the maximum temperature for which liquid water clusters reach the equilibrium melting line of bilayer ice as wetting bilayer clusters. Increasing water-surface attraction stabilizes the pancake-like wetting state of liquid clusters leading to larger T{sub B}{sup max} for the flat non-hydrogen bonding surfaces of this study. The findings of this study should be of relevance for the understanding of ice formation by deposition mode on carbonaceous atmospheric particles, including soot.« less

Investigating structural details of lipid-cholesterol-A β interactions

NASA Astrophysics Data System (ADS)

Rai, Durgesh; Anunciado, Divina; Heller, William; O'Neill, Hugh; Urban, Volker; Qian, Shuo

2015-03-01

Alzheimer's disease (AD) is the most common form of dementia and is predicted to affect 1 in 85 people around the world by 2050. Amyloid beta (A β) -peptide, a peptide composed of 40- 42 amino acids that is the product of cleavage from the amyloid precursor protein (APP), is regarded to play a major role in the development of AD. In addition, accumulating evidence points to a positive association between cholesterol and AD. Here, we present results from our studies about A β-peptide and cholesterol in bilayer by small-angle neutron scattering (SANS) using a combination of dimyristoyl, phosphocholine (DMPC) and partially deuterated cholesterol (cholesterol-d7) with and without A β. We compare the results using grazing incidence and transmission SANS on lipid bilayer films and unilamellar vesicles respectively. The structural details on vesicles and bilayers work in conjunction with the circular dichroism on peptide in solution and oriented circular dichroism in bilayer films. The studies confirm a positive association of A β with the membrane layers. The results from different studies will be compared and contrasted in presentation.

Effects of Ether vs. Ester Linkage on Lipid Bilayer Structure and Water Permeability

PubMed Central

Guler, S. Deren; Ghosh, D. Dipon; Pan, Jianjun; Matthai, John C.; Zeidel, Mark L.; Nagle, John F.; Tristram-Nagle, Stephanie

2009-01-01

The structure and water permeability of bilayers composed of the ether linked lipid, dihexadecylphosphatidylcholine (DHPC), were studied and compared with the ester linked lipid, dipalmitoylphosphaditdylcholine (DPPC). Wide angle x-ray scattering on oriented bilayers in the fluid phase indicate that the area per lipid A is slightly larger for DHPC than for DPPC. Low angle x-ray scattering yields A=65.1Å2 for DHPC at 48°C. LAXS data provide the bending modulus, KC=4.2×10−13erg, and the Hamaker parameter H=7.2×10−14erg for the van der Waals attractive interaction between neighboring bilayers. For the low temperature phases with ordered hydrocarbon chains, we confirm the transition from a tilted Lß’ gel phase to an untilted, interdigitated LßI phase as the sample hydrates at 20°C. Our measurement of water permeability, Pf=0.022 cm/s at 48 °C for fluid phase DHPC is slightly smaller than that of DPPC, (Pf=0.027 cm/s) at 50 °C, consistent with our triple slab theory of permeability. PMID:19416724

Changes in lipid bilayer structure caused by the helix-to-sheet transition of an HIV-1 gp41 fusion peptide derivative

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heller, William T.; Rai, Durgesh K.

HIV-1, like other enveloped viruses, undergoes fusion with the cell membrane to infect it. Viral coat proteins are thought to bind the virus to the membrane and actively fuse the viral and cellular membranes together. The actual molecular mechanism of fusion is challenging to visualize, resulting in the use of model systems. In this paper, the bilayer curvature modifying properties of a synthetic variant of the HIV-1 gp41 fusion peptide with lipid bilayer vesicles composed of a mixture of dimyristoyl phosphatidylcholine (DMPC) and dimyristoyl phosphatidylserine (DMPS) were studied. In 7:3 DMPC:DMPS vesicles made with deuterium-labeled DMPC, the peptide was observedmore » to undergo a concentration-dependent conformational transition between an α-helix and an antiparallel β-sheet. Through the use of small-angle neutron scattering (SANS) and selective deuterium labeling, it was revealed that conformational transition of the peptide is also accompanied by a transition in the structure of the lipid bilayer. In addition to changes in the distribution of the lipid between the leaflets of the vesicle, the SANS data are consistent with two regions having different thicknesses. Finally, of the two different bilayer structures, the one corresponding to the smaller area fraction, being ~8% of the vesicle area, is much thicker than the remainder of the vesicle, which suggests that there are regions of localized negative curvature similar to what takes place at the point of contact between two membranes immediately preceding fusion.« less

Force Spectroscopy Reveals the Effect of Different Ions in the Nanomechanical Behavior of Phospholipid Model Membranes: The Case of Potassium Cation

PubMed Central

Redondo-Morata, Lorena; Oncins, Gerard; Sanz, Fausto

2012-01-01

How do metal cations affect the stability and structure of phospholipid bilayers? What role does ion binding play in the insertion of proteins and the overall mechanical stability of biological membranes? Investigators have used different theoretical and microscopic approaches to study the mechanical properties of lipid bilayers. Although they are crucial for such studies, molecular-dynamics simulations cannot yet span the complexity of biological membranes. In addition, there are still some experimental difficulties when it comes to testing the ion binding to lipid bilayers in an accurate way. Hence, there is a need to establish a new approach from the perspective of the nanometric scale, where most of the specific molecular phenomena take place. Atomic force microscopy has become an essential tool for examining the structure and behavior of lipid bilayers. In this work, we used force spectroscopy to quantitatively characterize nanomechanical resistance as a function of the electrolyte composition by means of a reliable molecular fingerprint that reveals itself as a repetitive jump in the approaching force curve. By systematically probing a set of bilayers of different composition immersed in electrolytes composed of a variety of monovalent and divalent metal cations, we were able to obtain a wealth of information showing that each ion makes an independent and important contribution to the gross mechanical resistance and its plastic properties. This work addresses the need to assess the effects of different ions on the structure of phospholipid membranes, and opens new avenues for characterizing the (nano)mechanical stability of membranes. PMID:22225799

Changes in lipid bilayer structure caused by the helix-to-sheet transition of an HIV-1 gp41 fusion peptide derivative

DOE PAGES

Heller, William T.; Rai, Durgesh K.

2017-01-16

HIV-1, like other enveloped viruses, undergoes fusion with the cell membrane to infect it. Viral coat proteins are thought to bind the virus to the membrane and actively fuse the viral and cellular membranes together. The actual molecular mechanism of fusion is challenging to visualize, resulting in the use of model systems. In this paper, the bilayer curvature modifying properties of a synthetic variant of the HIV-1 gp41 fusion peptide with lipid bilayer vesicles composed of a mixture of dimyristoyl phosphatidylcholine (DMPC) and dimyristoyl phosphatidylserine (DMPS) were studied. In 7:3 DMPC:DMPS vesicles made with deuterium-labeled DMPC, the peptide was observedmore » to undergo a concentration-dependent conformational transition between an α-helix and an antiparallel β-sheet. Through the use of small-angle neutron scattering (SANS) and selective deuterium labeling, it was revealed that conformational transition of the peptide is also accompanied by a transition in the structure of the lipid bilayer. In addition to changes in the distribution of the lipid between the leaflets of the vesicle, the SANS data are consistent with two regions having different thicknesses. Finally, of the two different bilayer structures, the one corresponding to the smaller area fraction, being ~8% of the vesicle area, is much thicker than the remainder of the vesicle, which suggests that there are regions of localized negative curvature similar to what takes place at the point of contact between two membranes immediately preceding fusion.« less

Lipid bilayers suspended on microfabricated supports

NASA Astrophysics Data System (ADS)

Ogier, Simon D.; Bushby, Richard J.; Cheng, Yaling; Cox, Tim I.; Evans, Stephen D.; Knowles, Peter F.; Miles, Robert E.; Pattison, Ian

2001-03-01

The plasma membrane, that exists as part of many animal and plant cells, is a regulator for the transport of ions and small molecules across cell boundaries. Two main components involved are the phospholipid bilayer and the transport proteins. This paper details the construction of a micromachined support for bilayers (MSB) as a first step towards the development of highly selective and highly sensitive ion-channel based biosensors. The device consists of a ~100 micrometer hole in a polymeric support above a cavity that can hold ~25 nL of electrolyte. Electrodes attached to the structure allow the resistance of the membranes to be measured using d.c. conductivity. The MSB is made in two halves, using SU8 ultra-thick resist, which are subsequently bonded together to make the final structure. A layer of gold, surrounding the aperture, enables self-assembled monolayers of alkanethiols to be used to make the polymeric structure biocompatible. Lipid membranes have been formed over these holes with resistances comparable with those of natural membranes >10 MOhmcm^2. The ion-channel gramicidin has successfully been incorporated into the bilayer and its activity monitored. It is proposed that this type of device could be used not only for studying membrane transport phenomena but also as part of an ion-channel based biosensor.

DSC and EPR investigations on effects of cholesterol component on molecular interactions between paclitaxel and phospholipid within lipid bilayer membrane.

PubMed

Zhao, Lingyun; Feng, Si-Shen; Kocherginsky, Nikolai; Kostetski, Iouri

2007-06-29

Differential scanning calorimetry (DSC) and electron paramagnetic resonance spectroscopy (EPR) were applied to investigate effects of cholesterol component on molecular interactions between paclitaxel, which is one of the best antineoplastic agents found from nature, and dipalmitoylphosphatidylcholine (DPPC) within lipid bilayer vesicles (liposomes), which could also be used as a model cell membrane. DSC analysis showed that incorporation of paclitaxel into the DPPC bilayer causes a reduction in the cooperativity of bilayer phase transition, leading to a looser and more flexible bilayer structure. Including cholesterol component in the DPPC/paclitaxel mixed bilayer can facilitate the molecular interaction between paclitaxel and lipid and make the tertiary system more stable. EPR analysis demonstrated that both of paclitaxel and cholesterol have fluidization effect on the DPPC bilayer membranes although cholesterol has more significant effect than paclitaxel does. The reduction kinetics of nitroxides by ascorbic acid showed that paclitaxel can inhibit the reaction by blocking the diffusion of either the ascorbic acid or nitroxide molecules since the reaction is tested to be a first order one. Cholesterol can remarkably increase the reduction reaction speed. This research may provide useful information for optimizing liposomal formulation of the drug as well as for understanding the pharmacology of paclitaxel.

Measuring excess free energies of self-assembled membrane structures.

PubMed

Norizoe, Yuki; Daoulas, Kostas Ch; Müller, Marcus

2010-01-01

Using computer simulation of a solvent-free, coarse-grained model for amphiphilic membranes, we study the excess free energy of hourglass-shaped connections (i.e., stalks) between two apposed bilayer membranes. In order to calculate the free energy by simulation in the canonical ensemble, we reversibly transfer two apposed bilayers into a configuration with a stalk in three steps. First, we gradually replace the intermolecular interactions by an external, ordering field. The latter is chosen such that the structure of the non-interacting system in this field closely resembles the structure of the original, interacting system in the absence of the external field. The absence of structural changes along this path suggests that it is reversible; a fact which is confirmed by expanded-ensemble simulations. Second, the external, ordering field is changed as to transform the non-interacting system from the apposed bilayer structure to two-bilayers connected by a stalk. The final external field is chosen such that the structure of the non-interacting system resembles the structure of the stalk in the interacting system without a field. On the third branch of the transformation path, we reversibly replace the external, ordering field by non-bonded interactions. Using expanded-ensemble techniques, the free energy change along this reversible path can be obtained with an accuracy of 10(-3)k(B)T per molecule in the n VT-ensemble. Calculating the chemical potential, we obtain the free energy of a stalk in the grandcanonical ensemble, and employing semi-grandcanonical techniques, we calculate the change of the excess free energy upon altering the molecular architecture. This computational strategy can be applied to compute the free energy of self-assembled phases in lipid and copolymer systems, and the excess free energy of defects or interfaces.

Graphite, graphene and the flat band superconductivity

NASA Astrophysics Data System (ADS)

Volovik, G. E.

2018-04-01

Superconductivity has been observed in bilayer graphene [1,2]. The main factor, which determines the mechanism of the formation of this superconductivity is the "magic angle" of twist of two graphene layers, at which the electronic band structure becomes nearly flat. The specific role played by twist and by the band flattening, has been earlier suggested for explanations of the signatures of room-temperature superconductivity observed in the highly oriented pyrolytic graphite (HOPG), when the quasi two-dimensional interfaces between the twisted domains are present. The interface contains the periodic array of misfit dislocations (analogs of the boundaries of the unit cell of the Moire superlattice in bilayer graphene), which provide the possible source of the flat band. This demonstrates that it is high time for combination of the theoretical and experimental efforts in order to reach the reproducible room-temperature superconductivity in graphite or in similar real or artificial materials.

The influence of hyaluronan on the structure of a DPPC-bilayer under high pressures.

PubMed

Zander, Thomas; Wieland, D C Florian; Raj, Akanksha; Wang, Min; Nowak, Benedikt; Krywka, Christina; Dėdinaitė, Andra; Claesson, Per Martin; Garamus, Vasil M; Schreyer, Andreas; Willumeit-Römer, Regine

2016-06-01

The superior lubrication properties of synovial joints have inspired many studies aiming at uncovering the molecular mechanisms which give rise to low friction and wear. However, the mechanisms are not fully understood yet, and, in particular, it has not been elucidated how the biolubricants present at the interface of cartilage respond to high pressures, which arise during high loads of joints. In this study we utilize a simple model system composed of two biomolecules that have been implied as being important for joint lubrication. It consists of a solid supported dipalmitoylphosphatidylcholin (DPPC) bilayer, which was formed via vesicles fusion on a flat Si wafer, and the anionic polysaccharide hyaluronan (HA). We first characterized the structure of the HA layer that adsorbed to the DPPC bilayers at ambient pressure and different temperatures using X-ray reflectivity (XRR) measurements. Next, XRR was utilized to evaluate the response of the system to high hydrostatic pressures, up to 2kbar (200MPa), at three different temperatures. By means of fluorescence microscopy images the distribution of DPPC and HA on the surface was visualized. Our data suggest that HA adsorbs to the headgroup region that is oriented towards the water side of the supported bilayer. Phase transitions of the bilayer in response to temperature and pressure changes were also observed in presence and absence of HA. Our results reveal a higher stability against high hydrostatic pressures for DPPC/HA composite layers compared to that of the DPPC bilayer in absence of HA. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular Dynamics of a Water-Lipid Bilayer Interface

NASA Technical Reports Server (NTRS)

Wilson, Michael A.; Pohorille, Andrew

1994-01-01

We present results of molecular dynamics simulations of a glycerol 1-monooleate bilayer in water. The total length of analyzed trajectories is 5ns. The calculated width of the bilayer agrees well with the experimentally measured value. The interior of the membrane is in a highly disordered fluid state. Atomic density profile, orientational and conformational distribution functions, and order parameters indicate that disorder increases toward the center of the bilayer. Analysis of out-of-plane thermal fluctuations of the bilayer surfaces occurring at the time scale of the present calculations reveals that the distribution of modes agrees with predictions of the capillary wave model. Fluctuations of both bilayer surfaces are uncorrelated, yielding Gaussian distribution of instantaneous widths of the membrane. Fluctuations of the width produce transient thinning defects in the bilayer which occasionally span almost half of the membrane. The leading mechanism of these fluctuations is the orientational and conformational motion of head groups rather than vertical motion of the whole molecules. Water considerably penetrates the head group region of the bilayer but not its hydrocarbon core. The total net excess dipole moment of the interfacial water points toward the aqueous phase, but the water polarization profile is non-monotonic. Both water and head groups significantly contribute to the surface potential across the interface. The calculated sign of the surface potential is in agreement with that from experimental measurements, but the value is markedly overestimated. The structural and electrical properties of the water-bilayer system are discussed in relation to membrane functions, in particular transport of ions and nonelectrolytes across membranes.

Understanding the interaction of block copolymers with DMPC lipid bilayer using coarse-grained molecular dynamics simulations.

PubMed

Hezaveh, Samira; Samanta, Susruta; De Nicola, Antonio; Milano, Giuseppe; Roccatano, Danilo

2012-12-13

In this paper, we present a computational model of the adsorption and percolation mechanism of poloxamers (poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) triblock copolymers) across a 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayer. A coarse-grained model was used to cope with the long time scale of the percolation process. The simulations have provided details of the interaction mechanism of Pluronics with lipid bilayer. In particular, the results have shown that polymer chains containing a PPO block with a length comparable to the DMPC bilayer thickness, such as P85, tends to percolate across the lipid bilayer. On the contrary, Pluronics with a shorter PPO chain, such as L64 and F38, insert partially into the membrane with the PPO block part while the PEO blocks remain in water on one side of the lipid bilayer. The percolation of the polymers into the lipid tail groups reduces the membrane thickness and increases the area per lipid. These effects are more evident for P85 than L64 or F38. Our findings are qualitatively in good agreement with published small-angle X-ray scattering experiments that have evidenced a thinning effect of Pluronics on the lipid bilayer as well as the role of the length of the PPO block on the permeation process of the polymer through the lipid bilayer. Our theoretical results complement the experimental data with a detailed structural and dynamic model of poloxamers at the interface and inside the lipid bilayer.

Normal vibrational modes of phospholipid bilayers observed by low-frequency Raman scattering

NASA Astrophysics Data System (ADS)

Surovtsev, N. V.; Dmitriev, A. A.; Dzuba, S. A.

2017-03-01

Low-frequency Raman spectra of multilamellar vesicles made either of 1-palmitoyl-2-oleoyl-s n -glycero-3-phosphocholine (POPC) or 1,2-dipalmitoyl-s n -glycero-3-phosphocholine (DPPC) have been studied in a wide temperature range. Below 0 ∘C two peaks are found at frequencies around 8-9 and 14 -17 c m -1 and attributed to the normal vibrational modes of the phospholipid bilayer, which are determined by the bilayer thickness and stiffness (elastic modulus). The spectral positions of the peaks depend on the temperature and the bilayer composition. It is suggested that the ratio of the intensities of the first and second peaks can serve as a measure of the interleaflet elastic coupling. The addition of cholesterol to the phospholipid bilayer leads to peak shift and broadening, which may be assigned to the composition heterogeneities commonly attributed to the lipid raft formation.

Nanoscale patterning controls inorganic-membrane interface structure

NASA Astrophysics Data System (ADS)

Almquist, Benjamin D.; Verma, Piyush; Cai, Wei; Melosh, Nicholas A.

2011-02-01

The ability to non-destructively integrate inorganic structures into or through biological membranes is essential to realizing full bio-inorganic integration, including arrayed on-chip patch-clamps, drug delivery, and biosensors. Here we explore the role of nanoscale patterning on the strength of biomembrane-inorganic interfaces. AFM measurements show that inorganic probes functionalized with hydrophobic bands with thicknesses complimentary to the hydrophobic lipid bilayer core exhibit strong attachment in the bilayer. As hydrophobic band thickness increases to 2-3 times the bilayer core the interfacial strength decreases, comparable to homogeneously hydrophobic probes. Analytical calculations and molecular dynamics simulations predict a transition between a `fused' interface and a `T-junction' that matches the experimental results, showing lipid disorder and defect formation for thicker bands. These results show that matching biological length scales leads to more intimate bio-inorganic junctions, enabling rational design of non-destructive membrane interfaces.The ability to non-destructively integrate inorganic structures into or through biological membranes is essential to realizing full bio-inorganic integration, including arrayed on-chip patch-clamps, drug delivery, and biosensors. Here we explore the role of nanoscale patterning on the strength of biomembrane-inorganic interfaces. AFM measurements show that inorganic probes functionalized with hydrophobic bands with thicknesses complimentary to the hydrophobic lipid bilayer core exhibit strong attachment in the bilayer. As hydrophobic band thickness increases to 2-3 times the bilayer core the interfacial strength decreases, comparable to homogeneously hydrophobic probes. Analytical calculations and molecular dynamics simulations predict a transition between a `fused' interface and a `T-junction' that matches the experimental results, showing lipid disorder and defect formation for thicker bands. These results show that matching biological length scales leads to more intimate bio-inorganic junctions, enabling rational design of non-destructive membrane interfaces. Electronic supplementary information (ESI) available: Breakthrough rate as a function of force plots for 5 nm, 10 nm and ∞-probes.. See DOI: 10.1039/c0nr00486c

Self-assembled lipid bilayer materials

DOEpatents

Sasaki, Darryl Y.; Waggoner, Tina A.; Last, Julie A.

2005-11-08

The present invention is a self-assembling material comprised of stacks of lipid bilayers formed in a columnar structure, where the assembly process is mediated and regulated by chemical recognition events. The material, through the chemical recognition interactions, has a self-regulating system that corrects the radial size of the assembly creating a uniform diameter throughout most of the structure. The materials form and are stable in aqueous solution. These materials are useful as structural elements for the architecture of materials and components in nanotechnology, efficient light harvesting systems for optical sensing, chemical processing centers, and drug delivery vehicles.

Single-Molecule Resolution of Antimicrobial Peptide Interactions with Supported Lipid A Bilayers.

PubMed

Nelson, Nathaniel; Schwartz, Daniel K

2018-06-05

The molecular interactions between antimicrobial peptides (AMPs) and lipid A-containing supported lipid bilayers were probed using single-molecule total internal reflection fluorescence microscopy. Hybrid supported lipid bilayers with lipid A outer leaflets and phospholipid (1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE)) inner leaflets were prepared and characterized, and the spatiotemporal trajectories of individual fluorescently labeled LL37 and Melittin AMPs were determined as they interacted with the bilayer surfaces comprising either monophosphoryl or diphosphoryl lipid A (from Escherichia coli) to determine the impact of electrostatic interactions. Large numbers of trajectories were obtained and analyzed to obtain the distributions of surface residence times and the statistics of the spatial trajectories. Interestingly, the AMP species were sensitive to subtle differences in the charge of the lipid, with both peptides diffusing more slowly and residing longer on the diphosphoryl lipid A. Furthermore, the single-molecule dynamics indicated a qualitative difference between the behavior of AMPs on hybrid Lipid A bilayers and on those composed entirely of DOPE. Whereas AMPs interacting with a DOPE bilayer exhibited two-dimensional Brownian diffusion with a diffusion coefficient of ∼1.7 μm 2 /s, AMPs adsorbed to the lipid A surface exhibited much slower apparent diffusion (on the order of ∼0.1 μm 2 /s) and executed intermittent trajectories that alternated between two-dimensional Brownian diffusion and desorption-mediated three-dimensional flights. Overall, these findings suggested that bilayers with lipid A in the outer leaflet, as it is in bacterial outer membranes, are valuable model systems for the study of the initial stage of AMP-bacterium interactions. Furthermore, single-molecule dynamics was sensitive to subtle differences in electrostatic interactions between cationic AMPs and monovalent or divalent anionic lipid A moieties. Copyright © 2018 Biophysical Society. All rights reserved.

Tunneling Spectroscopy of Quantum Hall States in Bilayer Graphene

NASA Astrophysics Data System (ADS)

Wang, Ke; Harzheim, Achim; Watanabe, Kenji; Taniguchi, Takashi; Kim, Philip

In the quantum Hall (QH) regime, ballistic conducting paths along the physical edges of a sample appear, leading to quantized Hall conductance and vanishing longitudinal magnetoconductance. These QH edge states are often described as ballistic compressible strips separated by insulating incompressible strips, the spatial profiles of which can be crucial in understanding the stability and emergence of interaction driven QH states. In this work, we present tunneling transport between two QH edge states in bilayer graphene. Employing locally gated device structure, we guide and control the separation between the QH edge states in bilayer graphene. Using resonant Landau level tunneling as a spectroscopy tool, we measure the energy gap in bilayer graphene as a function of displacement field and probe the emergence and evolution of incompressible strips.

Experimental study of the bending elasticity of charged lipid bilayers in aqueous solutions with pH5

NASA Astrophysics Data System (ADS)

Mitkova, D.; Stoyanova-Ivanova, A.; Ermakov, Yu A.; Vitkova, V.

2012-12-01

Exposure to high concentrations of contaminations due to air polluting gases, vapours and aerosols and possibly altering the normal pH in the body could lead to undesirable changes in the properties of biological cells. Here, we study experimentally the mechanical properties of synthetic phospholipid bilayers containing increasing molar fractions (up to 0.15) of charged lipid (synthetic phosphatidylserine) in aqueous solutions with controlled ionic strength and at pH 5, which is slightly lower than the physiological values of pH. Our observations in phase contrast and fluorescence testified to the coexistence of two phases in membranes for temperatures below 29°C. Micro-sized inhomogeneities in vesicle membranes were systematically observed at temperatures lower than 29°C and for molar fractions of phosphatidylserine in the bilayer higher than 0.1. For the quantitative determination of the membrane bending rigidity, we applied thermal fluctuation analysis of the shape of quasispherical lipid vesicles. As far as the liquid-crystalline state of the bilayer is a necessary condition for the application of the experimental method, only vesicles satisfying this requirement were processed for determination of their membrane bending rigidity. The value obtained for the bending modulus of bilayers with 0.15 molar content of charged lipid is about two times higher than the bending modulus of uncharged membranes in the same bathing solution. These findings are in qualitative agreement with our previous results for the bending rigidity of charged bilayers, measured by vesicle micromanipulation.

Effects of fullerene on lipid bilayers displaying different liquid ordering: a coarse-grained molecular dynamics study.

PubMed

Sastre, Judit; Mannelli, Ilaria; Reigada, Ramon

2017-11-01

The toxic effects and environmental impact of nanomaterials, and in particular of Fullerene particles, are matters of serious concern. It has been reported that fullerene molecules enter the cell membrane and occupy its hydrophobic region. Understanding the effects of carbon-based nanoparticles on biological membranes is therefore of critical importance to determine their exposure risks. We report on a systematic coarse-grained molecular dynamics study of the interaction of fullerene molecules with simple model cell membranes. We have analyzed bilayers consisting of lipid species with different degrees of unsaturation and a variety of cholesterol fractions. Addition of fullerene particles to phase-segregated ternary membranes is also investigated in the context of the lipid raft model for the organization of the cell membrane. Fullerene addition to lipid membranes modifies their structural properties like thickness, area and internal ordering of the lipid species, as well as dynamical aspects such as molecular diffusion and cholesterol flip-flop. Interestingly, we show that phase-segregating ternary lipid membranes accumulate fullerene molecules preferentially in the liquid-disordered domains promoting phase-segregation and domain alignment across the membrane. Lipid membrane internal ordering determines the behavior and distribution of fullerene particle, and this, in turn, determines the influence of fullerene on the membrane. Lipid membranes are good solvents of fullerene molecules, and in particular those with low internal ordering. Preference of fullerene molecules to be dissolved in the more disordered hydrophobic regions of a lipid bilayer and the consequent alteration of its phase behavior may have important consequences on the activity of biological cell membranes and on the bioconcentration of fullerene in living organisms. Copyright © 2017 Elsevier B.V. All rights reserved.

Structure and dynamics of Penetratin's association and translocation to a lipid bilayer

NASA Astrophysics Data System (ADS)

Ignacio J., General; Asciutto, Eliana K.

2017-03-01

Penetratin belongs to the important class of small and positively charged peptides, capable of entering cells. The determination of the optimal peptidic structure for translocation is challenging; results obtained so far are varied and dependent on several factors. In this work, we review the dynamics of association of Penetratin with a modeled dioleoyl-phosphatidylcholine (DOPC) lipid membrane using molecular dynamics simulations with last generation force fields. Penetratin's structural preferences are determined using a Markov state model. It is observed that the peptide retains a helical form in the membrane associated state, just as in water, with the exception of both termini which lose helicity, facilitating the interaction of terminal residues with the phosphate groups on the membrane's outer layer. The optimal orientation for insertion is found to be with the peptide's axis forming a small angle with the interface, and with R1 stretching toward the bilayer. The interaction between arginine side-chains and phosphate groups is found to be greater than the corresponding to lysine, mainly due to a higher number of hydrogen bonds between them. The free energy profile of translocation is qualitatively studied using Umbrella Sampling. It is found that there are different paths of penetration, that greatly differ in size of free energy barrier. The lowest path is compatible with residues R10 to K13 leading the way through the membrane and pulling the rest of the peptide. When the other side is reached, the C-terminus overtakes those residues, and finally breaks out of the membrane. The peptide's secondary structure during this traversal suffers some changes with respect to the association structure but, overall, conserves its helicity, with both termini in a more disordered state.

Dynamic Structure of Bombolitin II Bound to Lipid Bilayers as Revealed by Solid-state NMR and Molecular-Dynamics Simulation

PubMed Central

Toraya, Shuichi; Javkhlantugs, Namsrai; Mishima, Daisuke; Nishimura, Katsuyuki; Ueda, Kazuyoshi; Naito, Akira

2010-01-01

Bombolitin II (BLT2) is one of the hemolytic heptadecapeptides originally isolated from the venom of a bumblebee. Structure and orientation of BLT2 bound to 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) membranes were determined by solid-state 31P and 13C NMR spectroscopy. 31P NMR spectra showed that BLT2-DPPC membranes were disrupted into small particles below the gel-to-liquid crystalline phase transition temperature (Tc) and fused to form a magnetically oriented vesicle system where the membrane surface is parallel to the magnetic fields above the Tc. 13C NMR spectra of site-specifically 13C-labeled BLT2 at the carbonyl carbons were observed and the chemical shift anisotropies were analyzed to determine the dynamic structure of BLT2 bound to the magnetically oriented vesicle system. It was revealed that the membrane-bound BLT2 adopted an α-helical structure, rotating around the membrane normal with the tilt angle of the helical axis at 33°. Interatomic distances obtained from rotational-echo double-resonance experiments further showed that BLT2 adopted a straight α-helical structure. Molecular dynamics simulation performed in the BLT2-DPPC membrane system showed that the BLT2 formed a straight α-helix and that the C-terminus was inserted into the membrane. The α-helical axis is tilted 30° to the membrane normal, which is almost the same as the value obtained from solid-state NMR. These results suggest that the membrane disruption induced by BLT2 is attributed to insertion of BLT2 into the lipid bilayers. PMID:21081076

Inducing morphological changes in lipid bilayer membranes with microfabricated substrates

NASA Astrophysics Data System (ADS)

Liu, Fangjie; Collins, Liam F.; Ashkar, Rana; Heberle, Frederick A.; Srijanto, Bernadeta R.; Collier, C. Patrick

2016-11-01

Lateral organization of lipids and proteins into distinct domains and anchoring to a cytoskeleton are two important strategies employed by biological membranes to carry out many cellular functions. However, these interactions are difficult to emulate with model systems. Here we use the physical architecture of substrates consisting of arrays of micropillars to systematically control the behavior of supported lipid bilayers - an important step in engineering model lipid membrane systems with well-defined functionalities. Competition between attractive interactions of supported lipid bilayers with the underlying substrate versus the energy cost associated with membrane bending at pillar edges can be systematically investigated as functions of pillar height and pitch, chemical functionalization of the microstructured substrate, and the type of unilamellar vesicles used for assembling the supported bilayer. Confocal fluorescent imaging and AFM measurements highlight correlations that exist between topological and mechanical properties of lipid bilayers and lateral lipid mobility in these confined environments. This study provides a baseline for future investigations into lipid domain reorganization on structured solid surfaces and scaffolds for cell growth.

AB-stacked square-like bilayer ice in graphene nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Bai, Jaeil; Zeng, Xiao Cheng; Wu, HengAn

2016-08-10

Water, when constrained between two graphene sheets and under ultrahigh pressure, can manifest dramatic differences from its bulk counterparts such as the van der Waals pressure induced water-to-ice transformation, known as the metastability limit of two-dimensional (2D) liquid. Here, we present result of a new crystalline structure of bilayer ice with the AB-stacking order, observed from molecular dynamics simulations of constrained water. This AB-stacked bilayer ice (BL-ABI) is transformed from the puckered monolayer square-like ice (pMSI) under higher lateral pressure in the graphene nanocapillary at ambient temperature. BL-ABI is a proton-ordered ice with square-like pattern. The transition from pMSI to BL-ABI is through crystal-to-amorphous-to-crystal pathway with notable hysteresis-loop in the potential energy during the compression/decompression process, reflecting the compression/tensile limit of the 2D monolayer/bilayer ice. In a superheating process, the BL-ABI transforms into the AB-stacked bilayer amorphous ice with the square-like pattern.

Interplay between alkyl chain asymmetry and cholesterol addition in the rigid ion pair amphiphile bilayer systems

NASA Astrophysics Data System (ADS)

Huang, Fong-yin; Chiu, Chi-cheng

2017-01-01

Ion pair amphiphile (IPA), a molecular complex composed of a pair of cationic and anionic surfactants, has been proposed as a novel phospholipid substitute. Controlling the physical stability of IPA vesicles is important for its application developments such as cosmetic and drug deliveries. To investigate the effects of IPA alkyl chain combinations and the cholesterol additive on the structural and mechanical properties of IPA vesicular bilayers, we conducted a series of molecular dynamics studies on the hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS) and dodecyltrimethylammonium-hexadecylsulfate (DTMA-HS) IPA bilayers with cholesterol. We found that both IPA bilayers are in the gel phase at 298 K, consistent with experimental observations. Compared with the HTMA-DS system, the DTMA-HS bilayer has more disordered alkyl chains in the hydrophobic region. When adding cholesterol, it induces alkyl chain ordering around its rigid sterol ring. Yet, cholesterol increases the molecular areas for all species and disturbs the molecular packing near the hydrophilic region and the bilayer core. Cholesterol also promotes the alkyl chain mismatch between the IPA moieties, especially for the DTMA-HS bilayer. The combined effects lead to non-monotonically enhancement of the membrane mechanical moduli for both IPA-cholesterol systems. Furthermore, cholesterol can form H-bonds with the alkylsulfate and thus enhance the contribution of alkylsulfate to the overall mechanical moduli. Combined results provide valuable molecular insights into the roles of each IPA component and the cholesterol on modulating the IPA bilayer properties.

Cholesterol effect on water permeability through DPPC and PSM lipid bilayers: a molecular dynamics study.

PubMed

Saito, Hiroaki; Shinoda, Wataru

2011-12-29

Water permeability of two different lipid bilayers of dipalmitoylphosphatidylcholine (DPPC) and palmitoylsphingomyelin (PSM) in the absence and presence of cholesterol (0-50 mol %) have been studied by molecular dynamics simulations to elucidate the molecular mechanism of the reduction in water leakage across the membranes by the addition of cholesterol. An enhanced free energy barrier was observed in these membranes with increased cholesterol concentration, and this was explained by the reduced cavity density around the cholesterol in the hydrophobic membrane core. There was an increase of trans conformers in the hydrophobic lipid chains adjacent to the cholesterol, which reduced the cavity density. The enhanced free energy barrier was found to be the main reason to reduce the water permeability with increased cholesterol concentration. At low cholesterol concentrations the PSM bilayer exhibited a higher free energy barrier than the DPPC bilayer for water permeation, while at greater than 30 mol % of cholesterol the difference became minor. This tendency for the PSM and DPPC bilayers to resemble each other at higher cholesterol concentrations was similar to commonly observed trends in several structural properties, such as order parameters, cross-sectional area per molecule, and cavity density profiles in the hydrophobic regions of bilayer membranes. These results demonstrate that DPPC and PSM bilayers with high cholesterol contents possess similar physical properties, which suggests that the solubility of cholesterol in these lipid bilayers has importance for an understanding of multicomponent lipid membranes with cholesterol. © 2011 American Chemical Society

Effect of intra-membrane C60 fullerenes on the modulus of elasticity and the mechanical resistance of gel and fluid lipid bilayers

NASA Astrophysics Data System (ADS)

Zhou, Jihan; Liang, Dehai; Contera, Sonia

2015-10-01

Penetration and partition of C60 to the lipid bilayer core are both relevant to C60 toxicity, and useful to realise C60 biomedical potential. A key aspect is the effect of C60 on bilayer mechanical properties. Here, we present an experimental study on the mechanical effect of the incorporation of C60 into the hydrophobic core of fluid and gel phase zwitterionic phosphatidylcholine (PC) lipid bilayers. We demonstrate its incorporation inside the hydrophobic lipid core and the effect on the packing of the lipids and the vesicle size using a combination of infrared (IR) spectroscopy, atomic force microscopy (AFM) and laser light scattering. Using AFM we measured the Young's modulus of elasticity (E) of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) in the absence (presence) of intra-membranous C60 at 24.5 °C. E of fluid phase supported bilayers is not altered by C60, but E increases with incorporation of C60 in gel phase bilayers. The increase is higher for longer hydrocarbon chains: 1.6 times for DPPC and 2 times for DSPC. However the mechanical resistance of gel phase bilayers of curved bilayered structures decreases with the incorporation of C60. Our combined results indicate that C60 causes a decrease in gel phase lipid mobility, i.e. an increase in membrane viscosity.

Electrophoretic deposition of bi-layered LSM/LSM-YSZ cathodes for solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Itagaki, Yoshiteru; Watanabe, Shinji; Yamaji, Tsuyoshi; Asamoto, Makiko; Yahiro, Hidenori; Sadaoka, Yoshihiko

2012-09-01

Bi-layered cathodes with the LSM/LSM-YSZ structure for solid oxide fuel cells were successfully formed on the carbon-sputtered surface of a YSZ sheet by electrophoretic deposition (EPD). The thicknesses of the first layer of LSM-YSZ (LY) and the second layer of La0.8Sr0.2MnO3 (LSM) could be controlled by adjusting the deposition time in the EPD process. The cathodic properties of the bi-layered structures were superior to those of the mono-layered structures, and were dependent on the thickness of each layer. Decreasing the thickness of the first layer and increasing that of the second layer tended to reduce both polarization and ohmic resistances. The optimal thickness of the first layer at the operating temperature of 600 °C was 4 μm, suggesting that an effective three-phase boundary was extended from the interface between the electrolyte and cathode film to around 4 μm thickness.

Xenon-ion-induced and thermal mixing of Co/Si bilayers and their interplay

NASA Astrophysics Data System (ADS)

Novaković, M.; Zhang, K.; Popović, M.; Bibić, N.; Hofsäss, H.; Lieb, K. P.

2011-05-01

Studies on ion-irradiated transition-metal/silicon bilayers demonstrate that interface mixing and silicide phase formation depend sensitively on the ion and film parameters, including the structure of the metal/Si interface. Thin Co layers e-gun evaporated to a thickness of 50 nm on Si(1 0 0) wafers were bombarded at room temperature with 400-keV Xe + ions at fluences of up to 3 × 10 16 cm -2. We used either crystalline or pre-amorphized Si wafers the latter ones prepared by 1.0-keV Ar-ion implantation. The as-deposited or Xe-ion-irradiated samples were then isochronally annealed at temperatures up to 700 °C. Changes of the bilayer structures induced by ion irradiation and/or annealing were investigated with RBS, XRD and HRTEM. The mixing rate for the Co/c-Si couples, Δ σ2/ Φ = 3.0(4) nm 4, is higher than the value expected for ballistic mixing and about half the value typical for spike mixing. Mixing of pre-amorphized Si is much weaker relative to crystalline Si wafers, contrary to previous results obtained for Fe/Si bilayers. Annealing of irradiated samples produces very similar interdiffusion and phase formation patterns above 400 °C as in the non-irradiated Co/Si bilayers: the phase evolution follows the sequence Co 2Si → CoSi → CoSi 2.

Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries.

PubMed

Zhu, YinBo; Wang, FengChao; Wu, HengAn

2016-08-07

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates that the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the "buckling failure" of the square-ice-nanotube columns, which is dominated by the lateral pressure.

Optical and Structural Characterization of ZnO/TiO2 Bilayer Thin Films Grown by Sol-Gel Spin Coating

NASA Astrophysics Data System (ADS)

Gareso, P. L.; Musfitasari; Juarlin, Eko

2018-03-01

Structural and optical properties of ZnO/TiO2 bilayers thin films have been investigated using x-ray diffraction (X-RD), scanning electron microscopy (SEM), and optical transmittance UV-Vis measurements. ZnO thin films were prepared by dissolving zinc acetate dehydrated into a solvent of ethanol and then added triethanolamin. In the case of TiO2 layers, tetraisoproxide was dissolved into ethanol and then added an acetate acid. The layer of ZnO was deposited first followed by TiO2 layer on a glass substrate using a spin coating technique. The ZnO/TiO2 bilayers were annealed at various temperatures from 300°C until 600°C for 60 minutes. The X-ray diffraction results show that there was an enhancement of the x-ray spectra as annealed temperature increased to 600°C in comparison to the samples that were annealed at 300°C. Based on the optical measurement of UV-Vis, the band gap energy of ZnO/TiO2 bilayer is around 3.2 eV at temperature of 300°C. This value is similar to the band gap energy of ZnO. SEM results show that there is no cluster in the surface of ZnO/TiO2 bilayer.

Generalization of the swelling method to measure the intrinsic curvature of lipids

NASA Astrophysics Data System (ADS)

Barragán Vidal, I. A.; Müller, M.

2017-12-01

Via computer simulation of a coarse-grained model of two-component lipid bilayers, we compare two methods of measuring the intrinsic curvatures of the constituting monolayers. The first one is a generalization of the swelling method that, in addition to the assumption that the spontaneous curvature linearly depends on the composition of the lipid mixture, incorporates contributions from its elastic energy. The second method measures the effective curvature-composition coupling between the apposing leaflets of bilayer structures (planar bilayers or cylindrical tethers) to extract the spontaneous curvature. Our findings demonstrate that both methods yield consistent results. However, we highlight that the two-leaflet structure inherent to the latter method has the advantage of allowing measurements for mixed lipid systems up to their critical point of demixing as well as in the regime of high concentration (of either species).

Synthetic polymers and biomembranes. How do they interact? Atomistic molecular dynamics simulation study of PEO in contact with a DMPC lipid bilayer.

PubMed

Pal, Sandeep; Milano, Giuseppe; Roccatano, Danilo

2006-12-28

The understanding of interactions of poly(ethylene glycol) (PEG) or poly(ethylene oxide) (PEO) with biological interfaces has important technological application in industry and in medicine. In this paper, structural and dynamical properties of PEO at the dimyristoylphospatidylcholine (DMPC) bilayer/water interface have been investigated by molecular dynamics (MD) and steered molecular dynamics (SMD) simulations. The structural properties of a PEO chain in bulk water, at the water/vacuum interface, and in the presence of the membrane were compared with available experimental data. The presence of a barrier for the PEO penetration into the DMPC bilayer has been found. A qualitative estimation of the barrier provided a value equal to approximately 19 kJ/mol, that is, 7 times the value of kT at 310 K.

Molecular Dynamics Simulations of PIP2 and PIP3 in Lipid Bilayers: Determination of Ring Orientation, and the Effects of Surface Roughness on a Poisson-Boltzmann Description

PubMed Central

Li, Zheng; Venable, Richard M.; Rogers, Laura A.; Murray, Diana; Pastor, Richard W.

2009-01-01

Abstract Molecular dynamics (MD) simulations of phosphatidylinositol (4,5)-bisphosphate (PIP2) and phosphatidylinositol (3,4,5)-trisphosphate (PIP3) in 1-palmitoyl 2-oleoyl phosphatidylcholine (POPC) bilayers indicate that the inositol rings are tilted ∼40° with respect to the bilayer surface, as compared with 17° for the P-N vector of POPC. Multiple minima were obtained for the ring twist (analogous to roll for an airplane). The phosphates at position 1 of PIP2 and PIP3 are within an Ångström of the plane formed by the phosphates of POPC; lipids in the surrounding shell are depressed by 0.5–0.8 Å, but otherwise the phosphoinositides do not substantially perturb the bilayer. Finite size artifacts for ion distributions are apparent for systems of ∼26 waters/lipid, but, based on simulations with a fourfold increase of the aqueous phase, the phosphoinositide positions and orientations do not show significant size effects. Electrostatic potentials evaluated from Poisson-Boltzmann (PB) calculations show a strong dependence of potential height and ring orientation, with the maxima on the −25 mV surfaces (17.1 ± 0.1 Å for PIP2 and 19.4 ± 0.3 Å for PIP3) occurring near the most populated orientations from MD. These surfaces are well above the background height of 10 Å estimated for negatively charged cell membranes, as would be expected for lipids involved in cellular signaling. PB calculations on microscopically flat bilayers yield similar maxima as the MD-based (microscopically rough) systems, but show less fine structure and do not clearly indicate the most probable regions. Electrostatic free energies of interaction with pentalysine are also similar for the rough and flat systems. These results support the utility of a rigid/flat bilayer model for PB-based studies of PIP2 and PIP3 as long as the orientations are judiciously chosen. PMID:19580753

Assembly of RNA nanostructures on supported lipid bilayers

PubMed Central

Dabkowska, Aleksandra P.; Michanek, Agnes; Jaeger, Luc; Rabe, Michael; Chworos, Arkadiusz; Höök, Fredrik; Nylander, Tommy; Sparr, Emma

2014-01-01

The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nanostructures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces. PMID:25417592

Interfacial exchange interactions and magnetism of Ni2MnAl /Fe bilayers

NASA Astrophysics Data System (ADS)

Yanes, R.; Simon, E.; Keller, S.; Nagyfalusi, B.; Khmelevsky, S.; Szunyogh, L.; Nowak, U.

2017-08-01

Based on multiscale calculations combining ab initio methods with spin dynamics simulations, we perform a detailed study of the magnetic behavior of Ni2MnAl /Fe bilayers. Our simulations show that such a bilayer exhibits a small exchange bias effect when the Ni2MnAl Heusler alloy is in a disordered B2 phase. Additionally, we present an effective way to control the magnetic structure of the Ni2MnAl antiferromagnet, in the pseudo-ordered B2-I as well as the disordered B2 phases, via a spin-flop coupling to the Fe layer.

Synthesis of bilayer MoS2 and corresponding field effect characteristics

NASA Astrophysics Data System (ADS)

Fang, Mingxu; Feng, Yulin; Wang, Fang; Yang, Zhengchun; Zhang, Kailiang

2017-06-01

Two-dimensional transition-metal dichalcogenides such as MoS2 are promising materials for next-generation nano-electronic devices. The physical properties of MoS2 are determined by layer number according to the variation of band-gap. Here, we synthesize large-size bilayer-MoS2 with triangle and hexagonal nanosheets in one step by chemical vapor deposition, Monolayer and bilayer-MoS2 back-gate field effect transistors are also fabricated and the performance including mobility and on/off ratios are compared. The bilayer-MoS2 back-gate field effect transistor shows superior performance with field effect mobility of ∼21.27cm2V-1s-1, and Ion/Ioff ratio of ∼3.9×107.

Direct Prediction of EPR Spectra from Lipid Bilayers: Understanding Structure and Dynamics in Biological Membranes.

PubMed

Catte, Andrea; White, Gaye F; Wilson, Mark R; Oganesyan, Vasily S

2018-06-02

Of the many biophysical techniques now being brought to bear on studies of membranes, electron paramagnetic resonance (EPR) of nitroxide spin probes was the first to provide information about both mobility and ordering in lipid membranes. Here, we report the first prediction of variable temperature EPR spectra of model lipid bilayers in the presence and absence of cholesterol from the results of large scale fully atomistic molecular dynamics (MD) simulations. Three types of structurally different spin probes were employed in order to study different parts of the bilayer. Our results demonstrate very good agreement with experiment and thus confirm the accuracy of the latest lipid force fields. The atomic resolution of the simulations allows the interpretation of the molecular motions and interactions in terms of their impact on the sensitive EPR line shapes. Direct versus indirect effects of cholesterol on the dynamics of spin probes are analysed. Given the complexity of structural organisation in lipid bilayers, the advantage of using a combined MD-EPR simulation approach is two-fold. Firstly, prediction of EPR line shapes directly from MD trajectories of actual phospholipid structures allows unambiguous interpretation of EPR spectra of biological membranes in terms of complex motions. Secondly, such an approach provides an ultimate test bed for the up-to-date MD simulation models employed in the studies of biological membranes, an area that currently attracts great attention. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Integrin Receptor in Biologically Relevant Bilayers: Insights from Molecular Dynamics Simulations.

PubMed

Kalli, Antreas C; Rog, Tomasz; Vattulainen, Ilpo; Campbell, Iain D; Sansom, Mark S P

2017-08-01

Integrins are heterodimeric (αβ) cell surface receptors that are potential therapeutic targets for a number of diseases. Despite the existence of structural data for all parts of integrins, the structure of the complete integrin receptor is still not available. We have used available structural data to construct a model of the complete integrin receptor in complex with talin F2-F3 domain. It has been shown that the interactions of integrins with their lipid environment are crucial for their function but details of the integrin/lipid interactions remain elusive. In this study an integrin/talin complex was inserted in biologically relevant bilayers that resemble the cell plasma membrane containing zwitterionic and charged phospholipids, cholesterol and sphingolipids to study the dynamics of the integrin receptor and its effect on bilayer structure and dynamics. The results of this study demonstrate the dynamic nature of the integrin receptor and suggest that the presence of the integrin receptor alters the lipid organization between the two leaflets of the bilayer. In particular, our results suggest elevated density of cholesterol and of phosphatidylserine lipids around the integrin/talin complex and a slowing down of lipids in an annulus of ~30 Å around the protein due to interactions between the lipids and the integrin/talin F2-F3 complex. This may in part regulate the interactions of integrins with other related proteins or integrin clustering thus facilitating signal transduction across cell membranes.

Experimental Investigation of the Electronic Properties of Twisted Bilayer Graphene by STM and STS

NASA Astrophysics Data System (ADS)

Yin, Longjing; Qiao, Jiabin; Wang, Wenxiao; Zuo, Weijie; He, Lin

The electronic properties of graphene multilayers depend sensitively on their stacking order. A twisted angle is treated as a unique degree of freedom to tune the electronic properties of graphene system. Here we study electronic structures of the twisted bilayers by scanning tunneling microscopy (STM) and spectroscopy (STS). We demonstrate that the interlayer coupling strength affects both the Van Hove singularities and the Fermi velocity of twisted bilayers dramatically. This removes the discrepancy about the Fermi velocity renormalization in the twisted bilayers and provides a consistent interpretation of all current data. Moreover, we report the experimental evidence for non-Abelian gauge potentials in twisted graphene bilayers by STM and STS. At a magic twisted angle, about 1.11°, a pronounced sharp peak is observed in the tunnelling spectra due to the action of the non-Abelian gauge fields. Because of the effective non-Abelian gauge fields, the rotation angle could transfer the charge carriers in the twisted bilayers from massless Dirac fermions into well localized electrons, or vice versa, efficiently. This provides a new route to tune the electronic properties of graphene systems, which will be essential in future graphene nanoelectronics.

Synthetic ion channels via self-assembly: a route for embedding porous polyoxometalate nanocapsules in lipid bilayer membranes.

PubMed

Carr, Rogan; Weinstock, Ira A; Sivaprasadarao, Asipu; Müller, Achim; Aksimentiev, Aleksei

2008-11-01

Porous polyoxometalate nanocapsules of Keplerate type are known to exhibit the functionality of biological ion channels; however, their use as an artificial ion channel is tempered by the high negative charge of the capsules, which renders their spontaneous incorporation into a lipid bilayer membrane unlikely. In this Letter we report coarse-grained molecular dynamics simulations that demonstrate a route for embedding negatively charged nanocapsules into lipid bilayer membranes via self-assembly. A homogeneous mixture of water, cationic detergent, and phospholipid was observed to spontaneously self-assemble around the nanocapsule into a layered, liposome-like structure, where the nanocapsule was enveloped by a layer of cationic detergent followed by a layer of phospholipid. Fusion of such a layered liposome with a lipid bilayer membrane was observed to embed the nanocapsule into the lipid bilayer. The resulting assembly was found to remain stable even after the surface of the capsule was exposed to electrolyte. In the latter conformation, water was observed to flow into and out of the capsule as Na(+) cations entered, suggesting that a polyoxometalate nanocapsule can form a functional synthetic ion channel in a lipid bilayer membrane.

Synthetic Ion Channels via Self-Assembly: a Route for Embedding Porous Polyoxometalate Nanocapsules in Lipid Bilayer Membranes

PubMed Central

Carr, Rogan; Weinstock, Ira A.; Sivaprasadarao, Asipu; Müller, Achim; Aksimentiev, Aleksei

2010-01-01

Porous polyoxometalate nanocapsules of Keplerate type are known to exhibit the functionality of biological ion channels, however, their use as artificial ion channel is tempered by the high negative charge of the capsules, which renders their spontaneous incorporation into a lipid bilayer membrane unlikely. In this letter we report coarse-grained molecular dynamics simulations that demonstrate a route for embedding negatively charged nanocapsules into lipid bilayer membranes via self-assembly. A homogeneous mixture of water, cationic detergent, and phospholipid was observed to spontaneously self-assemble around the nanocapsule into a layered, liposome-like structure, where the nanocapsule was enveloped by a layer of cationic detergent followed by a layer of phospholipid. Fusion of such a layered liposome with a lipid bilayer membrane was observed to embed the nanocapsule into the lipid bilayer. The resulting assembly was found to remain stable even after the surface of the capsule was exposed to electrolyte. In the latter conformation, water was observed to flow into and out of the capsule as Na+ cations entered, suggesting that a polyoxometalate nanocapsule can form a functional synthetic ion channel in a lipid bilayer membrane. PMID:18844424

A computer simulation of free-volume distributions and related structural properties in a model lipid bilayer.

PubMed Central

Xiang, T X

1993-01-01

A novel combined approach of molecular dynamics (MD) and Monte Carlo simulations is developed to calculate various free-volume distributions as a function of position in a lipid bilayer membrane at 323 K. The model bilayer consists of 2 x 100 chain molecules with each chain molecule having 15 carbon segments and one head group and subject to forces restricting bond stretching, bending, and torsional motions. At a surface density of 30 A2/chain molecule, the probability density of finding effective free volume available to spherical permeants displays a distribution with two exponential components. Both pre-exponential factors, p1 and p2, remain roughly constant in the highly ordered chain region with average values of 0.012 and 0.00039 A-3, respectively, and increase to 0.049 and 0.0067 A-3 at the mid-plane. The first characteristic cavity size V1 is only weakly dependent on position in the bilayer interior with an average value of 3.4 A3, while the second characteristic cavity size V2 varies more dramatically from a plateau value of 12.9 A3 in the highly ordered chain region to 9.0 A3 in the center of the bilayer. The mean cavity shape is described in terms of a probability distribution for the angle at which the test permeant is in contact with one of and does not overlap with anyone of the chain segments in the bilayer. The results show that (a) free volume is elongated in the highly ordered chain region with its long axis normal to the bilayer interface approaching spherical symmetry in the center of the bilayer and (b) small free volume is more elongated than large free volume. The order and conformational structures relevant to the free-volume distributions are also examined. It is found that both overall and internal motions have comparable contributions to local disorder and couple strongly with each other, and the occurrence of kink defects has higher probability than predicted from an independent-transition model. Images FIGURE 1 PMID:8241390

Linear and Nonlinear Spectroscopic Probing of Solute Interactions with Chemically Modified Silica Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wirth, Mary J

Solar energy conversion through biology would provide a renewable and nonpolluting abundance of energy. The bacterium Halobacterium salinarum converts solar to electrical energy by virtue of a transmembrane protein, bacteriorhodopsin. This transmembrane protein pumps protons across a nonconducting bilayer upon irradiation with green light. The bacterium evolved to perform this function inefficiently. If we were able to understand this process to engineer this protein for efficiency, then inexpensive energy production could be achieved. There are tens of thousands of different types of halobacteria, giving the opportunity to study different efficiencies and relating these to the protein structures. Technology does notmore » yet exist to perform such screening. The goal of this research is to generate new separation technology that can ultimately enable such screening. This involves creating a method for separating oriented and functional transmembrane proteins that remain in an electrically insulating lipid bilayer, with aqueous solutions on either side of the bilayer. A pH change across the lipid bilayer upon irradiation of a known concentration of proteins would probe function. Differences in proton pumping efficiency for different proteins variants would provide structure-function information for engineering the proteins. A schematic diagram from the original proposal is shown here. The idea is that (a) a lipid bilayer supported on a hydrophilic polymer film will make the bilayer fluid, and (b) applying an electric field will cause electrophoretic migration of the transmembrane proteins. We demonstrated this concept experimentally in a paper that was published just after this new grant period started (Lipid Bilayers on Polyacrylamide Brushes for Inclusion of Membrane Proteins, Emily A. Smith, Jason W. Coym, Scott M. Cowell, Victor J. Hruby, Henry I. Yamamura, Mary J. Wirth, Langmuir, 21, 9644-9650, 2005). The electrophoretic mobility was slow (10{sup -8} cm{sup 2}/Vs), and we project that a two order of magnitude increase would make this a practical tool. We are investigating two ways of improving electrophoretic mobility: better polymer supports, and a novel nanoporous medium that suspends the bilayer over free solution.« less

Probing Lipid Bilayers under Ionic Imbalance.

PubMed

Lin, Jiaqi; Alexander-Katz, Alfredo

2016-12-06

Biological membranes are normally under a resting transmembrane potential (TMP), which originates from the ionic imbalance between extracellular fluids and cytosols, and serves as electric power storage for cells. In cell electroporation, the ionic imbalance builds up a high TMP, resulting in the poration of cell membranes. However, the relationship between ionic imbalance and TMP is not clearly understood, and little is known about the effect of ionic imbalance on the structure and dynamics of biological membranes. In this study, we used coarse-grained molecular dynamics to characterize a dipalmitoylphosphatidylcholine bilayer system under ionic imbalances ranging from 0 to ∼0.06 e charges per lipid (e/Lip). We found that the TMP displayed three distinct regimes: 1) a linear regime between 0 and 0.045 e/Lip, where the TMP increased linearly with ionic imbalance; 2) a yielding regime between ∼0.045 and 0.060 e/Lip, where the TMP displayed a plateau; and 3) a poration regime above ∼0.060 e/Lip, where we observed pore formation within the sampling time (80 ns). We found no structural changes in the linear regime, apart from a nonlinear increase in the area per lipid, whereas in the yielding regime the bilayer exhibited substantial thinning, leading to an excess of water and Na + within the bilayer, as well as significant misalignment of the lipid tails. In the poration regime, lipid molecules diffused slightly faster. We also found that the fluid-to-gel phase transition temperature of the bilayer dropped below the normal value with increased ionic imbalances. Our results show that a high ionic imbalance can substantially alter the essential properties of the bilayer, making the bilayer more fluid like, or conversely, depolarization of a cell could in principle lead to membrane stiffening. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Gate-tunable resonant tunneling in double bilayer graphene heterostructures.

PubMed

Fallahazad, Babak; Lee, Kayoung; Kang, Sangwoo; Xue, Jiamin; Larentis, Stefano; Corbet, Christopher; Kim, Kyounghwan; Movva, Hema C P; Taniguchi, Takashi; Watanabe, Kenji; Register, Leonard F; Banerjee, Sanjay K; Tutuc, Emanuel

2015-01-14

We demonstrate gate-tunable resonant tunneling and negative differential resistance in the interlayer current-voltage characteristics of rotationally aligned double bilayer graphene heterostructures separated by hexagonal boron nitride (hBN) dielectric. An analysis of the heterostructure band alignment using individual layer densities, along with experimentally determined layer chemical potentials indicates that the resonance occurs when the energy bands of the two bilayer graphene are aligned. We discuss the tunneling resistance dependence on the interlayer hBN thickness, as well as the resonance width dependence on mobility and rotational alignment.

Direct measurement of discrete valley and orbital quantum numbers in bilayer graphene.

PubMed

Hunt, B M; Li, J I A; Zibrov, A A; Wang, L; Taniguchi, T; Watanabe, K; Hone, J; Dean, C R; Zaletel, M; Ashoori, R C; Young, A F

2017-10-16

The high magnetic field electronic structure of bilayer graphene is enhanced by the spin, valley isospin, and an accidental orbital degeneracy, leading to a complex phase diagram of broken symmetry states. Here, we present a technique for measuring the layer-resolved charge density, from which we directly determine the valley and orbital polarization within the zero energy Landau level. Layer polarization evolves in discrete steps across 32 electric field-tuned phase transitions between states of different valley, spin, and orbital order, including previously unobserved orbitally polarized states stabilized by skew interlayer hopping. We fit our data to a model that captures both single-particle and interaction-induced anisotropies, providing a complete picture of this correlated electron system. The resulting roadmap to symmetry breaking paves the way for deterministic engineering of fractional quantum Hall states, while our layer-resolved technique is readily extendable to other two-dimensional materials where layer polarization maps to the valley or spin quantum numbers.The phase diagram of bilayer graphene at high magnetic fields has been an outstanding question, with orders possibly between multiple internal quantum degrees of freedom. Here, Hunt et al. report the measurement of the valley and orbital order, allowing them to directly reconstruct the phase diagram.

Engineering plant membranes using droplet interface bilayers.

PubMed

Barlow, N E; Smpokou, E; Friddin, M S; Macey, R; Gould, I R; Turnbull, C; Flemming, A J; Brooks, N J; Ces, O; Barter, L M C

2017-03-01

Droplet interface bilayers (DIBs) have become widely recognised as a robust platform for constructing model membranes and are emerging as a key technology for the bottom-up assembly of synthetic cell-like and tissue-like structures. DIBs are formed when lipid-monolayer coated water droplets are brought together inside a well of oil, which is excluded from the interface as the DIB forms. The unique features of the system, compared to traditional approaches (e.g., supported lipid bilayers, black lipid membranes, and liposomes), is the ability to engineer multi-layered bilayer networks by connecting multiple droplets together in 3D, and the capability to impart bilayer asymmetry freely within these droplet architectures by supplying droplets with different lipids. Yet despite these achievements, one potential limitation of the technology is that DIBs formed from biologically relevant components have not been well studied. This could limit the reach of the platform to biological systems where bilayer composition and asymmetry are understood to play a key role. Herein, we address this issue by reporting the assembly of asymmetric DIBs designed to replicate the plasma membrane compositions of three different plant species; Arabidopsis thaliana , tobacco, and oats, by engineering vesicles with different amounts of plant phospholipids, sterols and cerebrosides for the first time. We show that vesicles made from our plant lipid formulations are stable and can be used to assemble asymmetric plant DIBs. We verify this using a bilayer permeation assay, from which we extract values for absolute effective bilayer permeation and bilayer stability. Our results confirm that stable DIBs can be assembled from our plant membrane mimics and could lead to new approaches for assembling model systems to study membrane translocation and to screen new agrochemicals in plants.

Does fluoride disrupt hydrogen bond network in cationic lipid bilayer? Time-dependent fluorescence shift of Laurdan and molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pokorna, Sarka; Jurkiewicz, Piotr; Hof, Martin, E-mail: martin.hof@jh-inst.cas.cz

2014-12-14

Time-dependent fluorescence shift (TDFS) of Laurdan embedded in phospholipid bilayers reports on hydration and mobility of the phospholipid acylgroups. Exchange of H{sub 2}O with D{sub 2}O prolongs the lifetime of lipid-water and lipid-water-lipid interactions, which is reflected in a significantly slower TDFS kinetics. Combining TDFS measurements in H{sub 2}O and D{sub 2}O hydrated bilayers with atomistic molecular dynamics (MD) simulations provides a unique tool for characterization of the hydrogen bonding at the acylgroup level of lipid bilayers. In this work, we use this approach to study the influence of fluoride anions on the properties of cationic bilayers composed of trimethylammonium-propanemore » (DOTAP). The results obtained for DOTAP are confronted with those for neutral phosphatidylcholine (DOPC) bilayers. Both in DOTAP and DOPC H{sub 2}O/D{sub 2}O exchange prolongs hydrogen-bonding lifetime and does not disturb bilayer structure. These results are confirmed by MD simulations. TDFS experiments show, however, that for DOTAP this effect is cancelled in the presence of fluoride ions. We interpret these results as evidence that strongly hydrated fluoride is able to steal water molecules that bridge lipid carbonyls. Consequently, when attracted to DOTAP bilayer, fluoride disrupts the local hydrogen-bonding network, and the differences in TDFS kinetics between H{sub 2}O and D{sub 2}O hydrated bilayers are no longer observed. A distinct behavior of fluoride is also evidenced by MD simulations, which show different lipid-ion binding for Cl{sup −} and F{sup −}.« less

Surface potentials measure ion concentrations near lipid bilayers during rapid solution changes.

PubMed Central

Laver, D R; Curtis, B A

1996-01-01

We describe a puffing method for changing solutions near one surface of lipid bilayers that allows simultaneous measurement of channel activity and extent of solution change at the bilayer surface. Ion adsorption to the lipid headgroups and screening of the bilayer surface charge by mobile ions provided a convenient probe for the ionic composition of the solution at the bilayer surface. Rapid ionic changes induced a shift in bilayer surface potential that generated a capacitive transient current under voltage-clamp conditions. This depended on the ion species and bilayer composition and was accurately described by the Stern-Gouy-Chapman theory. The time course of solute concentrations during solution changes could also be modeled by an exponential exchange of bath and puffing solutions with time constants ranging from 20 to 110 ms depending on the flow pressure. During changes in [Cs+] and [Ca2+] (applied separately or together) both the mixing model and capacitive currents predicted [Cs+] and [Ca2+] transients consistent with those determined experimentally from: 1) the known Cs(+)-dependent conductance of open ryanodine receptor channels and 2) the Ca(2+)-dependent gating of ryanodine receptor Ca2+ channels from cardiac and skeletal muscle. Images FIGURE 1 FIGURE 4 FIGURE 5 FIGURE 8 PMID:8842210

Biotinylated lipid bilayer disks as model membranes for biosensor analyses.

PubMed

Lundquist, Anna; Hansen, Søren B; Nordström, Helena; Danielson, U Helena; Edwards, Katarina

2010-10-15

The aim of this study was to investigate the potential of polyethylene glycol (PEG)-stabilized lipid bilayer disks as model membranes for surface plasmon resonance (SPR)-based biosensor analyses. Nanosized bilayer disks that included 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[biotinyl(polyethylene glycol)(2000)] (DSPE-PEG(2000)-biotin) were prepared and structurally characterized by cryo-transmission electron microscopy (cryo-TEM) imaging. The biotinylated disks were immobilized via streptavidin to three different types of sensor chips (CM3, CM4, and CM5) varying in their degree of carboxymethylation and thickness of the dextran matrix. The bilayer disks were found to interact with and bind stably to the streptavidin-coated sensor surfaces. As a first step toward the use of these bilayer disks as model membranes in SPR-based studies of membrane proteins, initial investigations were carried out with cyclooxygenases 1 and 2 (COX 1 and COX 2). Bilayer disks were preincubated with the respective protein and thereafter allowed to interact with the sensor surface. The signal resulting from the interaction was, in both cases, significantly enhanced as compared with the signal obtained when disks alone were injected over the surface. The results of the study suggest that bilayer disks constitute a new and promising type of model membranes for SPR-based biosensor studies. Copyright 2010 Elsevier Inc. All rights reserved.

Shock-induced nanobubble collapse and its applications

NASA Astrophysics Data System (ADS)

Vedadi, Mohammad Hossein

The shock-induced collapse of nanobubbles in water is investigated using molecular dynamics simulations based on a reactive force field. Monitoring the collapse of a cavitation nanobubble, we observe a focused nanojet at the onset of bubble shrinkage and a water hammer shock wave upon bubble collapse. The nanojet length scales linearly with the nanobubble radius, as observed in experiments on micron-to-millimeter size bubbles. The shock induces dramatic structural changes, including an ice-VII-like structural motif at a particle velocity of approximately 1 km/s. The incipient ice VII formation and the calculated Hugoniot curve are in good agreement with experimental results. Moreover, a substantial number of positive and negative ions appear when the nanojet hits the distal side of the nanobubble and the water hammer shock forms. Furthermore, two promising applications of shock-induced nanobubble collapse have been explored. Our simulations of poration in lipid bilayers due to shock-induced collapse of nanobubbles reveal penetration of nanojets into lipid bilayers. The nanojet impact generates shear flow of water on bilayer leaflets and pressure gradients across them, which transiently enhance the bilayer permeability by creating nanopores through which water molecules translocate across the bilayer. The effects of nanobubble size and temperature on the porosity of lipid bilayers are examined. Finally, the shock-induced collapse of CO2-filled nanobubbles in water is investigated. The energetic nanojet and high-pressure water hammer shock formed during and after collapse of the nanobubble trigger mechano-chemical H2O-CO2 reactions, some of which lead to splitting of water molecules. The dominant pathways through which splitting of water molecules occur are identified.

Electronic properties of BN-doped bilayer graphene and graphyne in the presence of electric field

NASA Astrophysics Data System (ADS)

Majidi, R.; Karami, A. R.

2013-11-01

In the present paper, we have used density functional theory to study electronic properties of bilayer graphene and graphyne doped with B and N impurities in the presence of electric field. It has been demonstrated that a band gap is opened in the band structures of the bilayer graphene and graphyne by B and N doping. We have also investigated influence of electric field on the electronic properties of BN-doped bilayer graphene and graphyne. It is found that the band gaps induced by B and N impurities are increased by applying electric field. Our results reveal that doping with B and N, and applying electric field are an effective method to open and control a band gap which is useful to design carbon-based next-generation electronic devices.

Magnetisation reversal in anisotropy graded Co/Pd multilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barton, C. W., E-mail: craig.barton-2@postgrad.manchester.ac.uk; Thomson, T.

2015-08-14

We demonstrate high precision controllability of the magnetization reversal nucleation process in [Co/Pd]{sub 8} multilayer films consisting of two sets of bilayers with high and low perpendicular anisotropy, respectively. The anisotropy of the entire film is set by the degree of Co/Pd interfacial mixing during deposition which provides fine control of the anisotropy of an individual bilayer in the multilayer stack. The relative number of each type of bilayer is used to select the magnetisation reversal behavior such that changing one bilayer changes the properties of the entire multilayer through anisotropy averaging. A simple extension to the sputtering protocol wouldmore » provide multilayer films with fully graded anisotropy, while maintaining a constant saturation magnetization opening new possibilities for the creation of highly engineered multilayer structures for spin torque devices and future magnetic recording media.« less

Delta-opiate DPDPE in magnetically oriented phospholipid micelles: binding and arrangement of aromatic pharmacophores.

PubMed Central

Rinaldi, F; Lin, M; Shapiro, M J; Petersheim, M

1997-01-01

D-Penicillamine(2,5)-enkephalin (DPDPE) is a potent opioid peptide that exhibits a high selectivity for the delta-opiate receptors. This zwitterionic peptide has been shown, by pulsed-field gradient 1H NMR diffusion studies, to have significant affinity for a zwitterionic phospholipid bilayer. The bilayer lipid is in the form of micelles composed of dihexanoylphosphatidylcholine (DHPC) and dimyristoylphosphatidylcholine (DMPC) mixtures, where the DMPC forms the bilayer structure. At high lipid concentration (25% w/w) these micelles orient in the magnetic field of an NMR spectrometer. The resulting 1H-13C dipolar couplings and chemical shift changes in the natural abundance 13C resonances for the Tyr and Phe aromatic rings were used to characterize the orientations in the bilayer micelles of these two key pharmacophores. Images FIGURE 1 FIGURE 8 PMID:9414244

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Chi-Yuan; Kausik, Ravinath; Han, Songi, E-mail: songi@chem.ucsb.edu

Elucidating the physical effect of cholesterol (Chol) on biological membranes is necessary towards rationalizing their structural and functional role in cell membranes. One of the debated questions is the role of hydration water in Chol-embedding lipid membranes, for which only little direct experimental data are available. Here, we study the hydration dynamics in a series of Chol-rich and depleted bilayer systems using an approach termed {sup 1}H Overhauser dynamic nuclear polarization (ODNP) NMR relaxometry that enables the sensitive and selective determination of water diffusion within 5–10 Å of a nitroxide-based spin label, positioned off the surface of the polar headgroupsmore » or within the nonpolar core of lipid membranes. The Chol-rich membrane systems were prepared from mixtures of Chol, dipalmitoyl phosphatidylcholine and/or dioctadecyl phosphatidylcholine lipid that are known to form liquid-ordered, raft-like, domains. Our data reveal that the translational diffusion of local water on the surface and within the hydrocarbon volume of the bilayer is significantly altered, but in opposite directions: accelerated on the membrane surface and dramatically slowed in the bilayer interior with increasing Chol content. Electron paramagnetic resonance (EPR) lineshape analysis shows looser packing of lipid headgroups and concurrently tighter packing in the bilayer core with increasing Chol content, with the effects peaking at lipid compositions reported to form lipid rafts. The complementary capability of ODNP and EPR to site-specifically probe the hydration dynamics and lipid ordering in lipid membrane systems extends the current understanding of how Chol may regulate biological processes. One possible role of Chol is the facilitation of interactions between biological constituents and the lipid membrane through the weakening or disruption of strong hydrogen-bond networks of the surface hydration layers that otherwise exert stronger repulsive forces, as reflected in faster surface water diffusivity. Another is the concurrent tightening of lipid packing that reduces passive, possibly unwanted, diffusion of ions and water across the bilayer.« less

Graphene Nanopore Support System for Simultaneous High-Resolution AFM Imaging and Conductance Measurements

PubMed Central

2015-01-01

Accurately defining the nanoporous structure and sensing the ionic flow across nanoscale pores in thin films and membranes has a wide range of applications, including characterization of biological ion channels and receptors, DNA sequencing, molecule separation by nanoparticle films, sensing by block co-polymers films, and catalysis through metal–organic frameworks. Ionic conductance through nanopores is often regulated by their 3D structures, a relationship that can be accurately determined only by their simultaneous measurements. However, defining their structure–function relationships directly by any existing techniques is still not possible. Atomic force microscopy (AFM) can image the structures of these pores at high resolution in an aqueous environment, and electrophysiological techniques can measure ion flow through individual nanoscale pores. Combining these techniques is limited by the lack of nanoscale interfaces. We have designed a graphene-based single-nanopore support (∼5 nm thick with ∼20 nm pore diameter) and have integrated AFM imaging and ionic conductance recording using our newly designed double-chamber recording system to study an overlaid thin film. The functionality of this integrated system is demonstrated by electrical recording (<10 pS conductance) of suspended lipid bilayers spanning a nanopore and simultaneous AFM imaging of the bilayer. PMID:24581087

Open and closed conformations of two SpoIIAA-like proteins (YP_749275.1 and YP_001095227.1) provide insights into membrane association and ligand binding

PubMed Central

Kumar, Abhinav; Lomize, Andrei; Jin, Kevin K.; Carlton, Dennis; Miller, Mitchell D.; Jaroszewski, Lukasz; Abdubek, Polat; Astakhova, Tamara; Axelrod, Herbert L.; Chiu, Hsiu-Ju; Clayton, Thomas; Das, Debanu; Deller, Marc C.; Duan, Lian; Feuerhelm, Julie; Grant, Joanna C.; Grzechnik, Anna; Han, Gye Won; Klock, Heath E.; Knuth, Mark W.; Kozbial, Piotr; Krishna, S. Sri; Marciano, David; McMullan, Daniel; Morse, Andrew T.; Nigoghossian, Edward; Okach, Linda; Reyes, Ron; Rife, Christopher L.; Sefcovic, Natasha; Tien, Henry J.; Trame, Christine B.; van den Bedem, Henry; Weekes, Dana; Xu, Qingping; Hodgson, Keith O.; Wooley, John; Elsliger, Marc-André; Deacon, Ashley M.; Godzik, Adam; Lesley, Scott A.; Wilson, Ian A.

2010-01-01

The crystal structures of the proteins encoded by the YP_749275.1 and YP_001095227.1 genes from Shewanella frigidimarina and S. loihica, respectively, have been determined at 1.8 and 2.25 Å resolution, respectively. These proteins are members of a novel family of bacterial proteins that adopt the α/β SpoIIAA-like fold found in STAS and CRAL-TRIO domains. Despite sharing 54% sequence identity, these two proteins adopt distinct conformations arising from different dispositions of their α2 and α3 helices. In the ‘open’ conformation (YP_001095227.1), these helices are 15 Å apart, leading to the creation of a deep nonpolar cavity. In the ‘closed’ structure (YP_749275.1), the helices partially unfold and rearrange, occluding the cavity and decreasing the solvent-exposed hydrophobic surface. These two complementary structures are reminiscent of the conformational switch in CRAL-TRIO carriers of hydrophobic compounds. It is suggested that both proteins may associate with the lipid bilayer in their ‘open’ monomeric state by inserting their amphiphilic helices, α2 and α3, into the lipid bilayer. These bacterial proteins may function as carriers of nonpolar substances or as interfacially activated enzymes. PMID:20944218

Nanoporous Au structures by dealloying Au/Ag thermal- or laser-dewetted bilayers on surfaces

NASA Astrophysics Data System (ADS)

Ruffino, F.; Torrisi, V.; Grillo, R.; Cacciato, G.; Zimbone, M.; Piccitto, G.; Grimaldi, M. G.

2017-03-01

Nanoporous Au attracts great technological interest and it is a promising candidate for optical and electrochemical sensors. In addition to nanoporous Au leafs and films, recently, interest was focused on nanoporous Au micro- and nano-structures on surfaces. In this work we report on the study of the characteristics of nanoporous Au structures produced on surfaces. We developed the following procedures to fabricate the nanoporous Au structures: we deposited thin Au/Ag bilayers on SiO2 or FTO (fluorine-doped tin oxide) substrates with thickness xAu and xAg of the Au and Ag layers; we induced the alloying and dewetting processes of the bilayers by furnace annealing processes of the bilayers deposited on SiO2 and by laser irradiations of the bilayers deposited on FTO; the alloying and dewetting processes result in the formation of AuxAgy alloy sub-micron particles being x and y tunable by xAu and xAg. These particles are dealloyed in HNO3 solution to remove the Ag atoms. We obtain, so, nanoporous sub-micron Au particles on the substrates. Analyzing the characteristics of these particles we find that: a) the size and shape of the particles depend on the nature of the dewetting process (solid-state dewetting on SiO2, molten-state dewetting on FTO); b) the porosity fraction of the particles depends on how the alloying process is reached: about 32% of porosity for the particles fabricated by the furnace annealing at 900 °C, about 45% of porosity for the particles fabricated by the laser irradiation at 0.5 J/cm2, in both cases independently on the Ag concentration in the alloy; c) After the dealloying process the mean volume of the Au particles shrinks of about 39%; d) After an annealing at 400 °C the nanoporous Au particles reprise their initial volume while the porosity fraction is reduced. Arguments to justify these behaviors are presented.

Laurdan spectrum decomposition as a tool for the analysis of surface bilayer structure and polarity: a study with DMPG, peptides and cholesterol.

PubMed

Lúcio, Aline D; Vequi-Suplicy, Cíntia C; Fernandez, Roberto M; Lamy, M Teresa

2010-03-01

The highly hydrophobic fluorophore Laurdan (6-dodecanoyl-2-(dimethylaminonaphthalene)) has been widely used as a fluorescent probe to monitor lipid membranes. Actually, it monitors the structure and polarity of the bilayer surface, where its fluorescent moiety is supposed to reside. The present paper discusses the high sensitivity of Laurdan fluorescence through the decomposition of its emission spectrum into two Gaussian bands, which correspond to emissions from two different excited states, one more solvent relaxed than the other. It will be shown that the analysis of the area fraction of each band is more sensitive to bilayer structural changes than the largely used parameter called Generalized Polarization, possibly because the latter does not completely separate the fluorescence emission from the two different excited states of Laurdan. Moreover, it will be shown that this decomposition should be done with the spectrum as a function of energy, and not wavelength. Due to the presence of the two emission bands in Laurdan spectrum, fluorescence anisotropy should be measured around 480 nm, to be able to monitor the fluorescence emission from one excited state only, the solvent relaxed state. Laurdan will be used to monitor the complex structure of the anionic phospholipid DMPG (dimyristoyl phosphatidylglycerol) at different ionic strengths, and the alterations caused on gel and fluid membranes due to the interaction of cationic peptides and cholesterol. Analyzing both the emission spectrum decomposition and anisotropy it was possible to distinguish between effects on the packing and on the hydration of the lipid membrane surface. It could be clearly detected that a more potent analog of the melanotropic hormone alpha-MSH (Ac-Ser(1)-Tyr(2)-Ser(3)-Met(4)-Glu(5)-His(6)-Phe(7)-Arg(8)-Trp(9)-Gly(10)-Lys(11)-Pro(12)-Val(13)-NH(2)) was more effective in rigidifying the bilayer surface of fluid membranes than the hormone, though the hormone significantly decreases the bilayer surface hydration.

Dynamic behavior of ultra large graphene-based membranes using electrothermal transduction

NASA Astrophysics Data System (ADS)

Al-mashaal, A. K.; Wood, G. S.; Torin, A.; Mastropaolo, E.; Newton, M. J.; Cheung, R.

2017-12-01

This letter reports an experimental study of an electrothermal actuator made from an ultra-large graphene-based bilayer thin film with a diameter to thickness aspect ratio of ˜10 000. Suspended thin films consisting of multilayer graphene and 350-500 nm-thick Poly(methyl methacrylate) have been transferred over circular cavities with a diameter of 3.5 mm. The use of bilayer materials with different mechanical and thermal properties results in thin film structures that can be induced to vibrate mechanically under the electrothermal transduction mechanism. The dynamic response of the bilayer has been investigated electrothermally by driving the structures with a combination of alternating current and direct current actuation voltages ( Va c and Vd c) and characterizing their resonant frequencies. It has been found that the bilayer thin film structure behaves as a membrane. In addition, the actuation configurations affect not only the amplitude of vibration but also the tuning of the resonant frequency of the vibrating membranes. The existence of Joule heating-induced tension lowers the mechanical stiffness of the membrane and hence shifts the resonant frequency downwards by -108187 ppm. A resonant frequency of 3.26 kHz with a vibration amplitude of 4.34 nm has been achieved for 350 nm-thick membranes under actuation voltages of 1 V of Va c and 8 V of Vd c.

Graphene-Based Polymer Bilayers with Superior Light-Driven Properties for Remote Construction of 3D Structures.

PubMed

Tang, Zhenhua; Gao, Ziwei; Jia, Shuhai; Wang, Fei; Wang, Yonglin

2017-05-01

3D structure assembly in advanced functional materials is important for many areas of technology. Here, a new strategy exploits IR light-driven bilayer polymeric composites for autonomic origami assembly of 3D structures. The bilayer sheet comprises a passive layer of poly(dimethylsiloxane) (PDMS) and an active layer comprising reduced graphene oxides (RGOs), thermally expanding microspheres (TEMs), and PDMS. The corresponding fabrication method is versatile and simple. Owing to the large volume expansion of the TEMs, the two layers exhibit large differences in their coefficients of thermal expansion. The RGO-TEM-PDMS/PDMS bilayers can deflect toward the PDMS side upon IR irradiation via the cooperative effect of the photothermal effect of the RGOs and the expansion of the TEMs, and exhibit excellent light-driven, a large bending deformation, and rapid responsive properties. The proposed RGO-TEM-PDMS/PDMS composites with excellent light-driven bending properties are demonstrated as active hinges for building 3D geometries such as bidirectionally folded columns, boxes, pyramids, and cars. The folding angle (ranging from 0° to 180°) is well-controlled by tuning the active hinge length. Furthermore, the folded 3D architectures can permanently preserve the deformed shape without energy supply. The presented approach has potential in biomedical devices, aerospace applications, microfluidic devices, and 4D printing.

Probing the mechanism of fusion in a two-dimensional computer simulation.

PubMed Central

Chanturiya, Alexandr; Scaria, Puthurapamil; Kuksenok, Oleksandr; Woodle, Martin C

2002-01-01

A two-dimensional (2D) model of lipid bilayers was developed and used to investigate a possible role of membrane lateral tension in membrane fusion. We found that an increase of lateral tension in contacting monolayers of 2D analogs of liposomes and planar membranes could cause not only hemifusion, but also complete fusion when internal pressure is introduced in the model. With a certain set of model parameters it was possible to induce hemifusion-like structural changes by a tension increase in only one of the two contacting bilayers. The effect of lysolipids was modeled as an insertion of a small number of extra molecules into the cis or trans side of the interacting bilayers at different stages of simulation. It was found that cis insertion arrests fusion and trans insertion has no inhibitory effect on fusion. The possibility of protein participation in tension-driven fusion was tested in simulation, with one of two model liposomes containing a number of structures capable of reducing the area occupied by them in the outer monolayer. It was found that condensation of these structures was sufficient to produce membrane reorganization similar to that observed in simulations with "protein-free" bilayers. These data support the hypothesis that changes in membrane lateral tension may be responsible for fusion in both model phospholipid membranes and in biological protein-mediated fusion. PMID:12023230

Characterization of the Structure and Membrane Interaction of the Antimicrobial Peptides Aurein 2.2 and 2.3 from Australian Southern Bell Frogs

PubMed Central

Pan, Yeang-Ling; Cheng, John T.-J.; Hale, John; Pan, Jinhe; Hancock, Robert E. W.; Straus, Suzana K.

2007-01-01

The structure and membrane interaction of the antimicrobial peptide aurein 2.2 (GLFDIVKKVVGALGSL-CONH2), aurein 2.3 (GLFDIVKKVVGAIGSL-CONH2), both from Litoria aurea, and a carboxy C-terminal analog of aurein 2.3 (GLFDIVKKVVGAIGSL-COOH) were studied to determine which features of this class of peptides are key to activity. Circular dichroism and solution-state NMR data indicate that all three peptides adopt an α-helical structure in the presence of trifluoroethanol or lipids such as 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and a 1:1 mixture of DMPC and 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)] (DMPG). Oriented circular dichroism was used to determine the orientation of the peptides in lipid bilayers over a range of concentrations (peptide/lipid molar ratios (P/L) = 1:15–1:120) in DMPC and 1:1 DMPC/DMPG, in the liquid crystalline state. The results demonstrate that in DMPC all three peptides are surface adsorbed over a range of low peptide concentrations but insert into the bilayers at high peptide concentrations. This finding is corroborated by 31P-solid-state NMR data of the three peptides in DMPC, which shows that at high peptide concentrations the peptides perturb the membrane. Oriented circular dichroism data of the aurein peptides in 1:1 DMPC/DMPG, on the other hand, show that the peptides with amidated C-termini readily insert into the membrane bilayers over the concentration range studied (P/L = 1:15–1:120), whereas the aurein 2.3 peptide with a carboxy C-terminus inserts at a threshold concentration of P/L* between 1:80 and 1:120. Overall, the data presented here suggest that all three peptides studied interact with phosphatidylcholine membranes in a manner which is similar to aurein 1.2 and citropin 1.1, as reported in the literature, with no correlation to the reported activity. On the other hand, both aurein 2.2 and aurein 2.3 behave similarly in phosphatidylcholine/phosphatidylglycerol (PC/PG) membranes, whereas aurein 2.3-COOH inserts less readily. As this does not correlate with reported activities, minimal inhibitory concentrations of the three peptides against Staphylococcus aureus (strain C622, ATCC 25923) and Staphylococcus epidermidis (strain C621—clinical isolate) were determined. The correlation between structure, membrane interaction, and activity are discussed in light of these results. PMID:17259271

Characterization of the structure and membrane interaction of the antimicrobial peptides aurein 2.2 and 2.3 from Australian southern bell frogs.

PubMed

Pan, Yeang-Ling; Cheng, John T-J; Hale, John; Pan, Jinhe; Hancock, Robert E W; Straus, Suzana K

2007-04-15

The structure and membrane interaction of the antimicrobial peptide aurein 2.2 (GLFDIVKKVVGALGSL-CONH(2)), aurein 2.3 (GLFDIVKKVVGAIGSL-CONH(2)), both from Litoria aurea, and a carboxy C-terminal analog of aurein 2.3 (GLFDIVKKVVGAIGSL-COOH) were studied to determine which features of this class of peptides are key to activity. Circular dichroism and solution-state NMR data indicate that all three peptides adopt an alpha-helical structure in the presence of trifluoroethanol or lipids such as 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and a 1:1 mixture of DMPC and 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)] (DMPG). Oriented circular dichroism was used to determine the orientation of the peptides in lipid bilayers over a range of concentrations (peptide/lipid molar ratios (P/L) = 1:15-1:120) in DMPC and 1:1 DMPC/DMPG, in the liquid crystalline state. The results demonstrate that in DMPC all three peptides are surface adsorbed over a range of low peptide concentrations but insert into the bilayers at high peptide concentrations. This finding is corroborated by (31)P-solid-state NMR data of the three peptides in DMPC, which shows that at high peptide concentrations the peptides perturb the membrane. Oriented circular dichroism data of the aurein peptides in 1:1 DMPC/DMPG, on the other hand, show that the peptides with amidated C-termini readily insert into the membrane bilayers over the concentration range studied (P/L = 1:15-1:120), whereas the aurein 2.3 peptide with a carboxy C-terminus inserts at a threshold concentration of P/L* between 1:80 and 1:120. Overall, the data presented here suggest that all three peptides studied interact with phosphatidylcholine membranes in a manner which is similar to aurein 1.2 and citropin 1.1, as reported in the literature, with no correlation to the reported activity. On the other hand, both aurein 2.2 and aurein 2.3 behave similarly in phosphatidylcholine/phosphatidylglycerol (PC/PG) membranes, whereas aurein 2.3-COOH inserts less readily. As this does not correlate with reported activities, minimal inhibitory concentrations of the three peptides against Staphylococcus aureus (strain C622, ATCC 25923) and Staphylococcus epidermidis (strain C621--clinical isolate) were determined. The correlation between structure, membrane interaction, and activity are discussed in light of these results.

An ab initio study of the electronic structure of indium and gallium chalcogenide bilayers

NASA Astrophysics Data System (ADS)

Ayadi, T.; Debbichi, L.; Said, M.; Lebègue, S.

2017-09-01

Using first principle calculations, we have studied the structural and electronic properties of two dimensional bilayers of indium and gallium chalcogenides. With density functional theory corrected for van der Waals interactions, the different modes of stacking were investigated in a systematic way, and several of them were found to compete in energy. Then, their band structures were obtained with the GW approximation and found to correspond to indirect bandgap semiconductors with a small dependency on the mode of stacking. Finally, by analysing the electron density, it appeared that GaSe-InS is a promising system for electron-hole separation.

Langmuir-Blodgett films of random copolymers of fluoroalkyl(meth)acrylate and methacrylic acid: Fabrication and X-ray diffraction study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Safronov, V.; Feigin, L.A.; Budovskaya, L.D.

1994-12-31

Langmuir-Blodgett films of amphiphilic fluorinated copolymers were fabricated and studied by X-ray diffraction. Although these films show poor interlayer periodicity, they possess a uniform thickness even in the case of very thin films of one bilayer (22 {angstrom}). This feature was used to obtain complex LB structures (superlattices) with alteration of copolymer and fatty acid bilayers. X-ray diffraction data proved the regular periodical organization of these structures and allowed to calculate electron density distribution across the superlattices.

Neutron scattering from myelin revisited: bilayer asymmetry and water-exchange kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Denninger, Andrew R.; Demé, Bruno; Cristiglio, Viviana

2014-12-01

The structure of internodal myelin in the rodent central and peripheral nervous systems has been determined using neutron diffraction. The kinetics of water exchange in these tissues is also described. Rapid nerve conduction in the central and peripheral nervous systems (CNS and PNS, respectively) of higher vertebrates is brought about by the ensheathment of axons with myelin, a lipid-rich, multilamellar assembly of membranes. The ability of myelin to electrically insulate depends on the regular stacking of these plasma membranes and on the presence of a number of specialized membrane-protein assemblies in the sheath, including the radial component, Schmidt–Lanterman incisures andmore » the axo–glial junctions of the paranodal loops. The disruption of this fine-structure is the basis for many demyelinating neuropathies in the CNS and PNS. Understanding the processes that govern myelin biogenesis, maintenance and destabilization requires knowledge of myelin structure; however, the tight packing of internodal myelin and the complexity of its junctional specializations make myelin a challenging target for comprehensive structural analysis. This paper describes an examination of myelin from the CNS and PNS using neutron diffraction. This investigation revealed the dimensions of the bilayers and aqueous spaces of myelin, asymmetry between the cytoplasmic and extracellular leaflets of the membrane, and the distribution of water and exchangeable hydrogen in internodal multilamellar myelin. It also uncovered differences between CNS and PNS myelin in their water-exchange kinetics.« less

Reconciling structural and thermodynamic predictions using all-atom and coarse-grain force fields: the case of charged oligo-arginine translocation into DMPC bilayers.

PubMed

Hu, Yuan; Sinha, Sudipta Kumar; Patel, Sandeep

2014-10-16

Using the translocation of short, charged cationic oligo-arginine peptides (mono-, di-, and triarginine) from bulk aqueous solution into model DMPC bilayers, we explore the question of the similarity of thermodynamic and structural predictions obtained from molecular dynamics simulations using all-atom and Martini coarse-grain force fields. Specifically, we estimate potentials of mean force associated with translocation using standard all-atom (CHARMM36 lipid) and polarizable and nonpolarizable Martini force fields, as well as a series of modified Martini-based parameter sets. We find that we are able to reproduce qualitative features of potentials of mean force of single amino acid side chain analogues into model bilayers. In particular, modifications of peptide-water and peptide-membrane interactions allow prediction of free energy minima at the bilayer-water interface as obtained with all-atom force fields. In the case of oligo-arginine peptides, the modified parameter sets predict interfacial free energy minima as well as free energy barriers in almost quantitative agreement with all-atom force field based simulations. Interfacial free energy minima predicted by a modified coarse-grained parameter set are -2.51, -4.28, and -5.42 for mono-, di-, and triarginine; corresponding values from all-atom simulations are -0.83, -3.33, and -3.29, respectively, all in units of kcal/mol. We found that a stronger interaction between oligo-arginine and the membrane components and a weaker interaction between oligo-arginine and water are crucial for producing such minima in PMFs using the polarizable CG model. The difference between bulk aqueous and bilayer center states predicted by the modified coarse-grain force field are 11.71, 14.14, and 16.53 kcal/mol, and those by the all-atom model are 6.94, 8.64, and 12.80 kcal/mol; those are of almost the same order of magnitude. Our simulations also demonstrate a remarkable similarity in the structural aspects of the ensemble of configurations generated using the all-atom and coarse-grain force fields. Both resolutions show that oligo-arginine peptides adopt preferential orientations as they translocate into the bilayer. The guiding theme centers on charged groups maintaining coordination with polar and charged bilayer components as well as local water. We also observe similar behaviors related with membrane deformations.

Interaction between the NS4B amphipathic helix, AH2, and charged lipid headgroups alters membrane morphology and AH2 oligomeric state--Implications for the Hepatitis C virus life cycle.

PubMed

Ashworth Briggs, Esther L; Gomes, Rafael G B; Elhussein, Malaz; Collier, William; Findlow, I Stuart; Khalid, Syma; McCormick, Chris J; Williamson, Philip T F

2015-08-01

The non-structural protein 4B (NS4B) from Hepatitis C virus (HCV) plays a pivotal role in the remodelling of the host cell's membranes, required for the formation of the viral replication complex where genome synthesis occurs. NS4B is an integral membrane protein that possesses a number of domains vital for viral replication. Structural and biophysical studies have revealed that one of these, the second amphipathic N-terminal helix (AH2), plays a key role in these remodelling events. However, there is still limited understanding of the mechanism through which AH2 promotes these changes. Here we report on solid-state NMR and molecular dynamics studies that demonstrate that AH2 promotes the clustering of negatively charged lipids within the bilayer, a process that reduces the strain within the bilayer facilitating the remodelling of the lipid bilayer. Furthermore, the presence of negatively charged lipids within the bilayer appears to promote the disassociation of AH2 oligomers, highlighting a potential role for lipid recruitment in regulating NS protein interactions. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Anderson localization in Nb/Al superconducting bilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greco, M.; Lacquaniti, V.; Maggi, S.

2000-01-01

The authors have measured the temperature dependence of resistivity in relatively thick Nb/Al bilayers fabricated at room temperature, observing the decrease of {rho} for increasing T typical of Anderson localization in disordered systems. The authors report the experimental conditions which determine this behavior and compare it to theoretical models for localization in 3D systems.

Hexagonal boron nitride intercalated multi-layer graphene: a possible ultimate solution to ultra-scaled interconnect technology

NASA Astrophysics Data System (ADS)

Li, Yong-Jun; Sun, Qing-Qing; Chen, Lin; Zhou, Peng; Wang, Peng-Fei; Ding, Shi-Jin; Zhang, David Wei

2012-03-01

We proposed intercalation of hexagonal boron nitride (hBN) in multilayer graphene to improve its performance in ultra-scaled interconnects for integrated circuit. The effect of intercalated hBN layer in bilayer graphene is investigated using non-equilibrium Green's functions. We find the hBN intercalated bilayer graphene exhibit enhanced transport properties compared with pristine bilayer ones, and the improvement is attributed to suppression of interlayer scattering and good planar bonding condition of inbetween hBN layer. Based on these results, we proposed a via structure that not only benefits from suppressed interlayer scattering between multilayer graphene, but also sustains the unique electrical properties of graphene when many graphene layers are stacking together. The ideal current density across the structure can be as high as 4.6×109 A/cm2 at 1V, which is very promising for the future high-performance interconnect.

Thylakoid membrane landscape in the sixties: a tribute to Andrew Benson.

PubMed

Anderson, Jan M

2007-05-01

Prior to the 1960s, the model for the molecular structure of cell membranes consisted of a lipid bilayer held in place by a thin film of electrostatically-associated protein stretched over the bilayer surface: (the Danielli-Davson-Robertson "unit membrane" model). Andrew Benson, an expert in the lipids of chloroplast thylakoid membranes, questioned the relevance of the unit membrane model for biological membranes, especially for thylakoid membranes, instead of emphasizing evidence in favour of hydrophobic interactions of membrane lipids within complementary hydrophobic regions of membrane-spanning proteins. With Elliot Weier, Benson postulated a remarkable subunit lipoprotein monolayer model for thylakoids. Following the advent of freeze fracture microscopy and the fluid lipid-protein mosaic model by Singer and Nicolson, the subunits, membrane-spanning integral proteins, span a dynamic lipid bilayer. Now that high resolution X-ray structures of photosystems I and II are being revealed, the seminal contribution of Andrew Benson can be appreciated.

Mutual adaptation of a membrane protein and its lipid bilayer during conformational changes.

PubMed

Sonntag, Yonathan; Musgaard, Maria; Olesen, Claus; Schiøtt, Birgit; Møller, Jesper Vuust; Nissen, Poul; Thøgersen, Lea

2011-01-01

The structural elucidation of membrane proteins continues to gather pace, but we know little about their molecular interactions with the lipid environment or how they interact with the surrounding bilayer. Here, with the aid of low-resolution X-ray crystallography, we present direct structural information on membrane interfaces as delineated by lipid phosphate groups surrounding the sarco(endo)plasmic reticulum Ca(2+)-ATPase (SERCA) in its phosphorylated and dephosphorylated Ca(2+)-free forms. The protein-lipid interactions are further analysed using molecular dynamics simulations. We find that SERCA adapts to membranes of different hydrophobic thicknesses by inducing local deformations in the lipid bilayers and by undergoing small rearrangements of the amino-acid side chains and helix tilts. These mutually adaptive interactions allow smooth transitions through large conformational changes associated with the transport cycle of SERCA, a strategy that may be of general nature for many membrane proteins.

Interaction of tachykinins with phospholipid membranes: A neutron diffraction study

NASA Astrophysics Data System (ADS)

Darkes, Malcolm J. M.; Davies, Sarah M. A.; Bradshaw, Jeremy P.

Tachykinins are a group of peptides which bind to G-protein-coupled receptors. Receptor affinity appears to depend on different secondary structures of tachykinin which share the same hydrophobic carboxy-terminal sequence, FXGLM. Receptor activation is thought to be due to the carboxy-terminal submerging into the bilayer and the amino-terminal binding on the surface. Binding of tachykinins to phospholipid bilayers may take place both on the aqueous membrane surface and in the hydrophobic region. The two-state equilibrium appears to depend on the surface charge of the membrane. Deuterating substance P and neurokinin A at their carboxy-terminals, our results show two populations of label for each peptide. One is very close to the water-hydrocarbon interface, the other some 13 Å deeper. We report that the bilayer location of the two tachykinins is remarkably similar, thereby inferring that receptor specifity must be controlled by finer levels of structure.

Cholesterol orientation and tilt modulus in DMPC bilayers

PubMed Central

Khelashvili, George; Pabst, Georg; Harries, Daniel

2010-01-01

We performed molecular dynamics (MD) simulations of hydrated bilayers containing mixtures of dimyristoylphosphatidylcholine (DMPC) and Cholesterol at various ratios, to study the effect of cholesterol concentration on its orientation, and to characterize the link between cholesterol tilt and overall phospholipid membrane organization. The simulations show a substantial probability for cholesterol molecules to transiently orient perpendicular to the bilayer normal, and suggest that cholesterol tilt may be an important factor for inducing membrane ordering. In particular, we find that as cholesterol concentration increases (1%–40% cholesterol) the average cholesterol orientation changes in a manner strongly (anti)correlated with the variation in membrane thickness. Furthermore, cholesterol orientation is found to be determined by the aligning force exerted by other cholesterol molecules. To quantify this aligning field, we analyzed cholesterol orientation using, to our knowledge, the first estimates of the cholesterol tilt modulus χ from MD simulations. Our calculations suggest that the aligning field that determines χ is indeed strongly linked to sterol composition. This empirical parameter (χ) should therefore become a useful quantitative measure to describe cholesterol interaction with other lipids in bilayers, particularly in various coarse-grained force fields. PMID:20518573

Interdroplet bilayer arrays in millifluidic droplet traps from 3D-printed moulds.

PubMed

King, Philip H; Jones, Gareth; Morgan, Hywel; de Planque, Maurits R R; Zauner, Klaus-Peter

2014-02-21

In droplet microfluidics, aqueous droplets are typically separated by an oil phase to ensure containment of molecules in individual droplets of nano-to-picoliter volume. An interesting variation of this method involves bringing two phospholipid-coated droplets into contact to form a lipid bilayer in-between the droplets. These interdroplet bilayers, created by manual pipetting of microliter droplets, have proved advantageous for the study of membrane transport phenomena, including ion channel electrophysiology. In this study, we adapted the droplet microfluidics methodology to achieve automated formation of interdroplet lipid bilayer arrays. We developed a 'millifluidic' chip for microliter droplet generation and droplet packing, which is cast from a 3D-printed mould. Droplets of 0.7-6.0 μL volume were packed as homogeneous or heterogeneous linear arrays of 2-9 droplets that were stable for at least six hours. The interdroplet bilayers had an area of up to 0.56 mm(2), or an equivalent diameter of up to 850 μm, as determined from capacitance measurements. We observed osmotic water transfer over the bilayers as well as sequential bilayer lysis by the pore-forming toxin melittin. These millifluidic interdroplet bilayer arrays combine the ease of electrical and optical access of manually pipetted microdroplets with the automation and reproducibility of microfluidic technologies. Moreover, the 3D-printing based fabrication strategy enables the rapid implementation of alternative channel geometries, e.g. branched arrays, with a design-to-device time of just 24-48 hours.

Solid-stabilized emulsion formation using stearoyl lactylate coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Vengsarkar, Pranav S.; Roberts, Christopher B.

2014-10-01

Iron oxide nanoparticles can exhibit highly tunable physicochemical properties that are extremely important in applications such as catalysis, biomedicine and environmental remediation. The small size of iron oxide nanoparticles can be used to stabilize oil-in-water Pickering emulsions due to their high energy of adsorption at the interface of oil droplets in water. The objective of this work is to investigate the effect of the primary particle characteristics and stabilizing agent chemistry on the stability of oil-in-water Pickering emulsions. Iron oxide nanoparticles were synthesized by the co-precipitation method using stoichiometric amounts of Fe2+ and Fe3+ salts. Sodium stearoyl lactylate (SSL), a Food and Drug Administration approved food additive, was used to functionalize the iron oxide nanoparticles. SSL is useful in the generation of fat-in-water emulsions due to its high hydrophilic-lipophilic balance and its bilayer-forming capacity. Generation of a monolayer or a bilayer coating on the nanoparticles was controlled through systematic changes in reagent concentrations. The coated particles were then characterized using various analytical techniques to determine their size, their crystal structure and surface functionalization. The capacity of these bilayer coated nanoparticles to stabilize oil-in-water emulsions under various salt concentrations and pH values was also systematically determined using various characterization techniques. This study successfully demonstrated the ability to synthesize iron oxide nanoparticles (20-40 nm) coated with SSL in order to generate stable Pickering emulsions that were pH-responsive and resistant to significant destabilization in a saline environment, thereby lending themselves to applications in advanced oil spill recovery and remediation.

Evidence for magnetic-field-induced decoupling of superconducting bilayers in La 2-xCa 1+xCu 2O 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Ruidan; Schneeloch, J. A.; Chi, Hang

We report a study of magnetic susceptibility and electrical resistivity as a function of temperature and magnetic field in superconducting crystals of La 2-xCa 1+xCu 2O 6 with x = 0.10 and 0.15 and transition temperature Tmore » $$m\\atop{c}$$ = 54 K (determined from the susceptibility). When an external magnetic field is applied perpendicular to the CuO 2 bilayers, the resistive superconducting transition measured with currents flowing perpendicular to the bilayers is substantially lower than that found with currents flowing parallel to the bilayers. Intriguingly, this anisotropic behavior is quite similar to that observed for the magnetic irreversibility points with the field applied either perpendicular or parallel to the bilayers. We discuss the results in the context of other studies that have found evidence for the decoupling of superconducting layers induced by a perpendicular magnetic field.« less

Protein-membrane electrostatic interactions: Application of the Lekner summation technique

NASA Astrophysics Data System (ADS)

Juffer, André H.; Shepherd, Craig M.; Vogel, Hans J.

2001-01-01

A model has been developed to calculate the electrostatic interaction between biomolecules and lipid bilayers. The effect of ionic strength is included by means of explicit ions, while water is described as a background continuum. The bilayer is considered at the atomic level. The Lekner summation technique is employed to calculate the long-range electrostatic interactions. The new method is employed to estimate the electrostatic contribution to the free energy of binding of sandostatin, a cyclic eight-residue analogue of the peptide hormone somatostatin, to lipid bilayers with thermodynamic integration. Monte Carlo simulation techniques were employed to determine ion distributions and peptide orientations. Both neutral as well as negatively charged lipid bilayers were used. An error analysis to judge the quality of the computation is also presented. The applicability of the Lekner summation technique to combine it with computer simulation models that simulate the adsorption of peptides (and proteins) into the interfacial region of lipid bilayers is discussed.

Evidence for magnetic-field-induced decoupling of superconducting bilayers in La 2-xCa 1+xCu 2O 6

DOE PAGES

Zhong, Ruidan; Schneeloch, J. A.; Chi, Hang; ...

2018-04-24

We report a study of magnetic susceptibility and electrical resistivity as a function of temperature and magnetic field in superconducting crystals of La 2-xCa 1+xCu 2O 6 with x = 0.10 and 0.15 and transition temperature Tmore » $$m\\atop{c}$$ = 54 K (determined from the susceptibility). When an external magnetic field is applied perpendicular to the CuO 2 bilayers, the resistive superconducting transition measured with currents flowing perpendicular to the bilayers is substantially lower than that found with currents flowing parallel to the bilayers. Intriguingly, this anisotropic behavior is quite similar to that observed for the magnetic irreversibility points with the field applied either perpendicular or parallel to the bilayers. We discuss the results in the context of other studies that have found evidence for the decoupling of superconducting layers induced by a perpendicular magnetic field.« less

Finite-size effects and magnetic exchange coupling in thin CoO layers

NASA Astrophysics Data System (ADS)

Ambrose, Thomas Francis

Finite size effects in CoO have been observed in CoO/SiOsb2 multilayers. The Neel temperatures of the CoO layers, as determined by dc susceptibility measurements, follow a finite-size scaling relation with a shift exponent lambda = 1.55 ± 0.05. This determined exponent is close to the theoretical value for finite size scaling in an Ising system. The value of the zero temperature correlation length has also been determined to be 18A, while antiferromagnetic ordering persists down to a CoO layer thickness of 10A. The properties of exchange biasing have been extensively studied in NiFe/CoO bilayers. The effects of the cooling field (Hsb{FC}), up to 50 kOe, on the resultant exchange field (Hsb{E}) and coercivity (Hsb{C}) have been examined. The value of Hsb{E} increases rapidly at low cooling fields (Hsb{FC} < 1kOe) and levels off for Hsb{FC} larger than 4 kOe. The value of Hsb{C} also depends upon Hsb{FC}, but less sensitively. The bilayer thickness also influences exchange biasing. We find that Hsb{E} varies inversely proprotional to both tsb{FM} and tsb{AF} where tsb{FM} and tsb{AF} are the ferromagnetic and antiferromagnetic layer thickness respectively. Because of the 1/tsb{AF}, the simple picture of interfacial coupling between ferromagnet and antiferromagnet spins appears to be inadequate. The assertion of long range coupling between ferromagnetic and antiferromagnetic layers has been verified by the observation of antiferromagnetic exchange coupling across spacer layers in NiFe/NM/CoO trilayers, where NM is a non-magnetic material. Exchange biasing has been observed in trilayers with metallic spacer layers up to 50A thick using Ag, Cu and Au, while no exchange field was observed for insulating spacer layers of any thickness using Alsb2Osb3, SiOsb2 and MgO. The temperature dependence of Hsb{E} and Hsb{C} and the effect of the deposition order have been studied in a series of bilayer (NiFe/CoO and CoO/NiFe) and trilayer (NiFe/CoO/NiFe) films. A profound difference in Hsb{E} was observed in samples with NiFe deposited on top of CoO compared to samples with CoO deposited on top of NiFe. When CoO is on top of NiFe Hsb{E} varies linearly with temperature, while for samples with NiFe on top of CoO Hsb{E} has a plateau followed by a rapid decrease. These distinct temperature dependences have been reproduced in NiFe/CoO/NiFe trilayers which contain both geometries. Structural analysis using Transmission Electron Microscopy indicate no apparent differences in the top and bottom interfaces. The angular dependence of the exchange coupling in a NiFe/CoO bilayer has been measured. Both Hsb{E} and Hsb{C} with unidirectional and uniaxial characteristics, respectively, are integral parts of the exchange coupling. The values of Hsb{E} can be expressed by a series of odd angle cosine terms, while the values of Hsb{C} can be expressed by a series of even angle cosine terms. Finally, exchange biasing has been used to "spin engineer" ferromagnetic layers in NiFe/CoO/NiFe trilayers. Four different spin structures have been observed. A phase diagram, for the four spin structures and the conditions with which each spin structure is obtained, has been determined. (Abstract shortened by UMI.)

Fabrication of TiO2/CuO photoelectrode with enhanced solar water splitting activity

NASA Astrophysics Data System (ADS)

Atabaev, Timur Sh.; Lee, Dae Hun; Hong, Nguyen Hoa

A bilayered TiO2/CuO photoelectrode was fabricated on a fluorine-doped tin oxide FTO substrate by spin-coating and pulsed laser deposition methods. The prepared bilayered system was assessed as a photoelectrode for solar water splitting. The fabricated TiO2/CuO photoelectrode exhibited a higher photocurrent density (0.022mA/cm2 at 1.23V vs. RHE) compared to bare TiO2 photoelectrode (0.013mA/cm2 at 1.23V vs. RHE). This photocurrent density enhancement was attributed to the improved charge separation combined with the improved sunlight harvesting efficiency of a bilayered structure.

Failure modes and materials design for biomechanical layer structures

NASA Astrophysics Data System (ADS)

Deng, Yan

Ceramic materials are finding increasing usage in the area of biomechanical replacements---dental crowns, hip and bone implants, etc.---where strength, wear resistance, biocompatibility, chemical durability and even aesthetics are critical issues. Aesthetic ceramic crowns have been widely used in dentistry to replace damaged or missing teeth. However, the failure rates of ceramic crowns, especially all-ceramic crowns, can be 1%˜6% per year, which is not satisfactory to patients. The materials limitations and underlying fracture mechanisms of these prostheses are not well understood. In this thesis, fundamental fracture and damage mechanisms in model dental bilayer and trilayer structures are studied. Principle failure modes are identified from in situ experimentation and confirmed by fracture mechanics analysis. In bilayer structures of ceramic/polycarbonate (representative of ceramic crown/dentin structure), three major damage sources are identified: (i) top-surface cone cracks or (ii) quasiplasticity, dominating in thick ceramic bilayers; (iii) bottom-surface radial cracks, dominating in thin ceramic bilayers. Critical load P for each damage mode are measured in six dental ceramics: Y-TZP zirconia, glass-infiltrated zirconia and alumina (InCeram), glass-ceramic (Empress II), Porcelain (Mark II and Empress) bonded to polymer substrates, as a function of ceramic thickness d in the range of 100 mum to 10 mm. P is found independent of d for mode (i) and (ii), but has a d 2 relations for mode (iii)---bottom surface radial cracking. In trilayer structures of glass/core-ceramic/polycarbonate (representing veneer porcelain/core/dentin structures), three inner fracture origins are identified: radial cracks from the bottom surface in the (i) first and (ii) second layers; and (iii) quasiplasticity in core-ceramic layer. The role of relative veneer/core thickness, d1/d 2 and materials properties is investigated for three core materials with different modulus (114--270GPa) and strength (400--1400MPa): Y-TZP zirconia, InCeram alumina and Empress II glass-ceramic. Explicit relations for the critical loads P to produce these different damage modes in bilayer and trilayer structures are developed in terms of basic material properties (modulus E, strength, hardness H and toughness T) and geometrical variables (thickness d and contact sphere radius r). These experimentally validated relations are used to design of optimal material combinations for improved fracture resistance and to predict mechanical performance of current dental materials.

Asymmetric distribution of charged lipids between the leaflets of a vesicle bilayer induced by melittin and alamethicin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qian, Shuo; Heller, William T

2011-01-01

Cellular membranes are complex mixtures of lipids, proteins, and other small molecules that provide functional, dynamic barriers between the cell and its environment, as well as between environments within the cell. The lipid composition of the membrane is highly specific and controlled in terms of both content and lipid localization. The membrane structure results from the complex interplay between the wide varieties of molecules present. Here, small-angle neutron scattering and selective deuterium labeling were used to probe the impact of the membrane-active peptides melittin and alamethicin on the structure of lipid bilayers composed of a mixture of the lipids dimyristoylmore » phosphatidylglycerol (DMPG) and chain-perdeuterated dimyristoyl phosphatidylcholine (DMPC). We found that both peptides enriched the outer leaflet of the bilayer with the negatively charged DMPG, creating an asymmetric distribution of lipids. The level of enrichment is peptide concentration-dependent and is stronger for melittin than it is for alamethicin. The enrichment between the inner and outer bilayer leaflets occurs at very low peptide concentrations and increases with peptide concentration, including when the peptide adopts a membrane-spanning, pore-forming state. The results suggest that these membrane-active peptides may have a secondary stressful effect on target cells at low concentrations that results from a disruption of the lipid distribution between the inner and outer leaflets of the bilayer that is independent of the formation of transmembrane pores.« less

Buckling failure of square ice-nanotube arrays constrained in graphene nanocapillaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, YinBo; Wang, FengChao, E-mail: wangfc@ustc.edu.cn; Wu, HengAn

Graphene confinement provides a new physical and mechanical environment with ultrahigh van der Waals pressure, resulting in new quasi-two-dimensional phases of few-layer ice. Polymorphic transition can occur in bilayer constrained water/ice system. Here, we perform a comprehensive study of the phase transition of AA-stacked bilayer water constrained within a graphene nanocapillary. The compression-limit and superheating-limit (phase) diagrams are obtained, based on the extensive molecular-dynamics simulations at numerous thermodynamic states. Liquid-to-solid, solid-to-solid, and solid-to-liquid-to-solid phase transitions are observed in the compression and superheating of bilayer water. Interestingly, there is a temperature threshold (∼275 K) in the compression-limit diagram, which indicates thatmore » the first-order and continuous-like phase transitions of bilayer water depend on the temperature. Two obviously different physical processes, compression and superheating, display similar structural evolution; that is, square ice-nanotube arrays (BL-VHDI) will bend first and then transform into bilayer triangular AA stacking ice (BL-AAI). The superheating limit of BL-VHDI exhibits local maxima, while that of BL-AAI increases monotonically. More importantly, from a mechanics point of view, we propose a novel mechanism of the transformation from BL-VHDI to BL-AAI, both for the compression and superheating limits. This structural transformation can be regarded as the “buckling failure” of the square-ice-nanotube columns, which is dominated by the lateral pressure.« less

A theoretical study of diffusional transport over the alveolar surfactant layer.

PubMed

Aberg, Christoffer; Sparr, Emma; Larsson, Marcus; Wennerström, Håkan

2010-10-06

In this communication, we analyse the passage of oxygen and carbon dioxide over the respiratory membrane. The lung surfactant membrane at the alveolar interface can have a very special arrangement, which affects the diffusional transport. We present a theoretical model for the diffusion of small molecules in membranes with a complex structure, and we specifically compare a membrane composed of a tubular bilayer network with a membrane consisting of a stack of bilayers. Oxygen and carbon dioxide differ in terms of their solubility in the aqueous and the lipid regions of the membrane, and we show that this difference clearly influences their transport properties in the different membrane structures. During normal respiration, the rate-limiting step for carbon dioxide transport is in the gas phase of the different compartments in the lung. For oxygen, on the other hand, the rate is limited by the transport between alveoli and the capillary blood vessels, including the lung surfactant membrane. In a membrane with a structure of a continuous tubular lipid network, oxygen transport is facilitated to a significant extent compared with the structure of aligned lipid bilayers. The model calculations in the present study show that transport of oxygen through the tubular structure is indeed ca 30 per cent faster than transport through a membrane composed of stacked bilayers. The tubular network will also facilitate the transport of apolar substances between the gas phase and the blood. Important examples are ethanol and other volatile liquids that can leave the blood through the lungs, and gaseous anaesthetics or volatile solvents that are inhaled. This exemplifies a new physiological role of a tubular lipid network in the lung surfactant membrane.

[Effect of core: dentin thickness ratio on the flexure strength of IPS Empress II heat-pressed all-ceramic restorative material].

PubMed

Liu, Yi-hong; Feng, Hai-lan; Bao, Yi-wang; Qiu, Yan

2007-02-18

To evaluate the effect of core:dentin thickness ratio on the flexure strength, fracture mode and origin of bilayered IPS Empress II ceramic composite specimens. IPS Empress II core ceramic, dentin porcelain and bilayered composite specimens with core:dentin thickness ratio of 2:1 and 1:1 were tested in three-point flexure strength. Mean strengths and standard deviations were determined. The optical microscopy was employed for identification of the fracture mode and origin. The flexure strength of dentin porcelain was the smallest(62.7 MPa), and the strength of bilayered composite specimens was smaller than single-layered core ceramic(190.2 MPa). The core: dentin ratio did not influence the strength of bilayered composite specimens. The frequency of occurrence of bilayered specimen delaminations was higher in the group of core: dentin thickness ratio of 1:1 than in the group of 2:1. IPS Empress II core ceramic was significantly stronger than veneering dentin porcelain. Core:dentin thickness ratio could significantly influence the fracture mode and origin, and bilayered IPS Empress II ceramic composite specimens showed little influence in the fracture strength.

Flexible bilayers with spontaneous curvature lead to lamellar gels and spontaneous vesicles

PubMed Central

Coldren, Bret A.; Warriner, Heidi; van Zanten, Ryan; Zasadzinski, Joseph A.; Sirota, Eric B.

2006-01-01

Mixtures of cetyltrimethylammonium tosylate (CTAT) and sodium dodecylbenzene sulfonate (SDBS) in water form a fluid lamellar phase at ≤40 wt % water but surprisingly turn into viscous gels at higher water fractions. The gels are characterized by spherulite and other bilayer defects consistent with a low bending elasticity, κ ∼ kBT, and a nonzero spontaneous curvature. Caillé analysis of the small-angle x-ray line shape confirms that for 7:3 wt:wt CTAT:SDBS bilayers at 50% water, κ = 0.62 ± 0.09 kBT and κ̄ = −0.9 ± 0.2 kBT. For 13:7 wt:wt CTAT:SDBS bilayers, the measured bending elasticity decreases with increasing water dilution in good agreement with predictions based on renormalization theory, giving κo = 0.28 kBT. These results show that surfactant mixing is sufficient to make κ ∼ kBT, which promotes strong, Helfrich-type repulsion between bilayers that can dominate the van der Waals attraction. These are necessary conditions for spontaneous vesicles formed at even higher water fractions to be equilibrium structures. PMID:16467142

Mechanical control of the electro-optical properties of monolayer and bilayer BC3 by applying the in-plane biaxial strain

NASA Astrophysics Data System (ADS)

Behzad, Somayeh

2017-11-01

Recently, a new two-dimensional (2D) material, the 2D BC3 crystal, has been synthesized. Here, the mechanical control of the electro-optical properties of monolayer and bilayer BC3 by applying the biaxial strain is investigated. The electronic structure calculations showed that the strain-free monolayer and bilayer BC3 are indirect band-gap semiconductors with band gap of 0.62 and 0.29 eV, respectively, where the conduction band minimum (CBM) is at the M point whereas the valence band maximum (VBM) is at the Γ point. The doubly degenerated bands in the monolayer BC3 are splitted in the bilayer BC3 due to the interlayer interactions. Both monolayer and bilayer BC3 remain indirect gap semiconductor under biaxial tensile strain and their band gaps increases with strain. On the other hand, by increasing the magnitude of tensile strain, the optical spectra shift to the lower energies and the static dielectric constant increases. These findings suggest the potential of strain-engineered 2D BC3 in electronic and optoelectronic device applications.

Lipid domains control myelin basic protein adsorption and membrane interactions between model myelin lipid bilayers

PubMed Central

Lee, Dong Woog; Banquy, Xavier; Kristiansen, Kai; Kaufman, Yair; Boggs, Joan M.; Israelachvili, Jacob N.

2014-01-01

The surface forces apparatus and atomic force microscope were used to study the effects of lipid composition and concentrations of myelin basic protein (MBP) on the structure of model lipid bilayers, as well as the interaction forces and adhesion between them. The lipid bilayers had a lipid composition characteristic of the cytoplasmic leaflets of myelin from “normal” (healthy) and “disease-like” [experimental allergic encephalomyelitis (EAE)] animals. They showed significant differences in the adsorption mechanism of MBP. MBP adsorbs on normal bilayers to form a compact film (3–4 nm) with strong intermembrane adhesion (∼0.36 mJ/m2), in contrast to its formation of thicker (7–8 nm) swelled films with weaker intermembrane adhesion (∼0.13 mJ/m2) on EAE bilayers. MBP preferentially adsorbs to liquid-disordered submicron domains within the lipid membranes, attributed to hydrophobic attractions. These results show a direct connection between the lipid composition of membranes and membrane–protein adsorption mechanisms that affects intermembrane spacing and adhesion and has direct implications for demyelinating diseases. PMID:24516125

The effect of the protein corona on the interaction between nanoparticles and lipid bilayers.

PubMed

Di Silvio, Desirè; Maccarini, Marco; Parker, Roger; Mackie, Alan; Fragneto, Giovanna; Baldelli Bombelli, Francesca

2017-10-15

It is known that nanoparticles (NPs) in a biological fluid are immediately coated by a protein corona (PC), composed of a hard (strongly bounded) and a soft (loosely associated) layers, which represents the real nano-interface interacting with the cellular membrane in vivo. In this regard, supported lipid bilayers (SLB) have extensively been used as relevant model systems for elucidating the interaction between biomembranes and NPs. Herein we show how the presence of a PC on the NP surface changes the interaction between NPs and lipid bilayers with particular care on the effects induced by the NPs on the bilayer structure. In the present work we combined Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) and Neutron Reflectometry (NR) experimental techniques to elucidate how the NP-membrane interaction is modulated by the presence of proteins in the environment and their effect on the lipid bilayer. Our study showed that the NP-membrane interaction is significantly affected by the presence of proteins and in particular we observed an important role of the soft corona in this phenomenon. Copyright © 2017 Elsevier Inc. All rights reserved.

Controlled release from bilayer-decorated magnetoliposomes via electromagnetic heating.

PubMed

Chen, Yanjing; Bose, Arijit; Bothun, Geoffrey D

2010-06-22

Nanoscale assemblies that can be activated and controlled through external stimuli represent a next stage in multifunctional therapeutics. We report the formation, characterization, and release properties of bilayer-decorated magnetoliposomes (dMLs) that were prepared by embedding small hydrophobic SPIO nanoparticles at different lipid molecule to nanoparticle ratios within dipalmitoylphosphatidylcholine (DPPC) bilayers. The dML structure was examined by cryogenic transmission electron microscopy and differential scanning calorimetry, and release was examined by carboxyfluorescein leakage. Nanoparticle heating using alternating current electromagnetic fields (EMFs) operating at radio frequencies provided selective release of the encapsulated molecule at low nanoparticle concentrations and under physiologically acceptable EMF conditions. Without radio frequency heating, spontaneous leakage from the dMLs decreased with increasing nanoparticle loading, consistent with greater bilayer stability and a decrease in the effective dML surface area due to aggregation. With radio frequency heating, the initial rate and extent of leakage increased significantly as a function of nanoparticle loading and electromagnetic field strength. The mechanism of release is attributed to a combination of bilayer permeabilization and partial dML rupture.

Influence of chain ordering on the selectivity of dipalmitoylphosphatidylcholine bilayer membranes for permeant size and shape.

PubMed Central

Xiang, T X; Anderson, B D

1998-01-01

The effects of lipid chain packing and permeant size and shape on permeability across lipid bilayers have been investigated in gel and liquid crystalline dipalmitoylphosphatidylcholine (DPPC) bilayers by a combined NMR line-broadening/dynamic light scattering method using seven short-chain monocarboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, and trimethylacetic acid) as permeants. The experimental permeability coefficients are compared with the predictions of a bulk solubility diffusion model in which the bilayer membrane is represented as a slab of bulk hexadecane. Deviations of the observed permeability coefficients (Pm) from the values predicted from solubility diffusion theory (Po) lead to the determination of a correction factor, the permeability decrement f (= Pm/Po), to account for the effects of chain ordering. The natural logarithm of f has been found to correlate linearly with the inverse of the bilayer free surface area with slopes of 25 +/- 2, 36 +/- 3, 45 +/- 8, 32 +/- 12, 33 +/- 4, 49 +/- 12, and 75 +/- 6 A2 for formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, and trimethylacetic acid, respectively. The slope, which measures the sensitivity of the permeability coefficient of a given permeant to bilayer chain packing, exhibits an excellent linear correlation (r = 0.94) with the minimum cross-sectional area of the permeant and a poor correlation (r = 0.59) with molecular volume, suggesting that in the bilayer interior the permeants prefer to move with their long principal axis along the bilayer normal. Based on these studies, a permeability model combining the effects of bilayer chain packing and permeant size and shape on permeability across lipid membranes is developed. PMID:9826590

Three Dimensional Architecture of Membrane-Embedded MscS in the Closed Conformation

PubMed Central

Vásquez, Valeria; Sotomayor, Marcos; Cortes, D. Marien; Roux, Benoît; Schulten, Klaus; Perozo, Eduardo

2009-01-01

The mechanosensitive channel of small conductance (MscS) is part of a coordinated response to osmotic challenges in E. coli. MscS opens as a result of membrane tension changes, thereby releasing small solutes and effectively acting as an osmotic safety valve. Both, the functional state depicted by its crystal structure and its gating mechanism remain unclear. Here, we combine site-directed spin labeling, electron paramagnetic resonance (EPR) spectroscopy, and molecular dynamics simulations with novel energy restraints based on experimental EPR data to investigate the native transmembrane and periplasmic molecular architecture of closed MscS in a lipid bilayer. In the closed conformation, MscS shows a more compact transmembrane domain than in the crystal structure, characterized by a realignment of the transmembrane segments towards the normal of the membrane. The previously unresolved NH2-terminus forms a short helical hairpin capping the extracellular ends of TM1 and TM2 and in close interaction with the bilayer interface. The present three-dimensional model of membrane-embedded MscS in the closed state represents a key step in determining the molecular mechanism of MscS gating. PMID:18343404

Study of the Interaction of the HIV-1 Fusion Peptide with Lipid Bilayer Membranes

NASA Astrophysics Data System (ADS)

Heller, William; Rai, Durgesh

HIV-1 undergoes fusion with the cell membrane through interactions between its coat proteins and the target cell. Visualization of fusion with sufficient detail to determine the molecular mechanism remains elusive. Here, the interaction between a synthetic variant of the HIV-1 gp41 fusion peptide with vesicles composed of dimyristoyl phosphatidylcholine (DMPC) and dimyristoyl phosphatidylserine (DMPS) was studied. The peptide was observed to undergo a concentration-dependent conformational transition between an α-helix and an antiparallel β-sheet that is accompanied by a transition in the structure of the lipid bilayer vesicle. The peptide changes the distribution of lipids between the vesicle leaflets. Further, it creates two regions having different thicknesses. The results shed new light on how the peptide modifies the membrane structure to favor fusion. A portion of this research was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U. S. Department of Energy. Research at Oak Ridge National Laboratory's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U. S. Department of Energy.

Lipid oxidation in bilayer liposomes induced by radicals from the surrounding water phases

NASA Astrophysics Data System (ADS)

Sprinz, H.; Brede, O.

1996-03-01

Some features of the radiation chemistry of organized assemblies were studied in aqueous dispersions of small unilamellar vesicles of egg yolk lecithin. The kinetics for the reaction of OH radicals with the bilayer was determined by pulse radiolysis. The conversion of OH radicals into N 3 radicals results in a remarkable reduction of the radiolysis of the hydrophylic part of the phospholipid and in an enhanced degradation of the most radiosensitive group of polyunsaturated fatty acid residues. The transverse proton relaxation of the choline head group is very sensitive to the radical attack on the bilayer.

Theory of passive proton conductance in lipid bilayers.

PubMed

Nagle, J F

1987-10-01

The large permeability of lipid bilayers to protons compared to other small ions calls for a special proton transport mechanism. At the present time, only mechanisms involving transient hydrogen-bonded chains of water can account for the experimental result that the conductance is nearly independent of pH. Three models involving transient hydrogen-bonded chains are discussed, including an outline of the kinetic calculations that lead to predictions of current versus voltage drop and current versus pH differences. These calculations can be compared to experiment to determine which, if any, of these models pertains to lipid bilayers.

Membrane-assisted growth of DNA origami nanostructure arrays.

PubMed

Kocabey, Samet; Kempter, Susanne; List, Jonathan; Xing, Yongzheng; Bae, Wooli; Schiffels, Daniel; Shih, William M; Simmel, Friedrich C; Liedl, Tim

2015-01-01

Biological membranes fulfill many important tasks within living organisms. In addition to separating cellular volumes, membranes confine the space available to membrane-associated proteins to two dimensions (2D), which greatly increases their probability to interact with each other and assemble into multiprotein complexes. We here employed two DNA origami structures functionalized with cholesterol moieties as membrane anchors--a three-layered rectangular block and a Y-shaped DNA structure--to mimic membrane-assisted assembly into hierarchical superstructures on supported lipid bilayers and small unilamellar vesicles. As designed, the DNA constructs adhered to the lipid bilayers mediated by the cholesterol anchors and diffused freely in 2D with diffusion coefficients depending on their size and number of cholesterol modifications. Different sets of multimerization oligonucleotides added to bilayer-bound origami block structures induced the growth of either linear polymers or two-dimensional lattices on the membrane. Y-shaped DNA origami structures associated into triskelion homotrimers and further assembled into weakly ordered arrays of hexagons and pentagons, which resembled the geometry of clathrin-coated pits. Our results demonstrate the potential to realize artificial self-assembling systems that mimic the hierarchical formation of polyhedral lattices on cytoplasmic membranes.

Boron doped Si rich oxide/SiO{sub 2} and silicon rich nitride/SiN{sub x} bilayers on molybdenum-fused silica substrates for vertically structured Si quantum dot solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Ziyun, E-mail: z.lin@unsw.edu.au; Wu, Lingfeng; Jia, Xuguang

2015-07-28

Vertically structured Si quantum dots (QDs) solar cells with molybdenum (Mo) interlayer on quartz substrates would overcome current crowding effects found in mesa-structured cells. This study investigates the compatibility between boron (B) doped Si QDs bilayers and Mo-fused silica substrate. Both Si/SiO{sub 2} and Si/SiN{sub x} based QDs bilayers were studied. The material compatibility under high temperature treatment was assessed by examining Si crystallinity, microstress, thin film adhesion, and Mo oxidation. It was observed that the presence of Mo interlayer enhanced the Si QDs size confinement, crystalline fraction, and QDs size uniformity. The use of B doping was preferred comparedmore » to phosphine (PH{sub 3}) doping studied previously in terms of better surface and interface properties by reducing oxidized spots on the film. Though crack formation due to thermal mismatch after annealing remained, methods to overcome this problem were proposed in this paper. Schematic diagram to fabricate full vertical structured Si QDs solar cells was also suggested.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morrow, Brian H.; Shen, Jana K.; Eike, David M.

Knowledge of the protonation behavior of pH-sensitive molecules in micelles and bilayers has significant implications in consumer product development and biomedical applications. However, the calculation of pK{sub a}’s in such environments proves challenging using traditional structure-based calculations. Here we apply all-atom constant pH molecular dynamics with explicit ions and titratable water to calculate the pK{sub a} of a fatty acid molecule in a micelle of dodecyl trimethylammonium chloride and liquid as well as gel-phase bilayers of diethyl ester dimethylammonium chloride. Interestingly, the pK{sub a} of the fatty acid in the gel bilayer is 5.4, 0.4 units lower than that inmore » the analogous liquid bilayer or micelle, despite the fact that the protonated carboxylic group is significantly more desolvated in the gel bilayer. This work illustrates the capability of all-atom constant pH molecular dynamics in capturing the delicate balance in the free energies of desolvation and Coulombic interactions. It also shows the importance of the explicit treatment of ions in sampling the protonation states. The ability to model dynamics of pH-responsive substrates in a bilayer environment is useful for improving fabric care products as well as our understanding of the side effects of anti-inflammatory drugs.« less

Geometry of phase-separated domains in phospholipid bilayers by diffraction-contrast electron microscopy.

PubMed Central

Hui, S W

1981-01-01

The sizes and shapes of solidus (gel) phase domains in the hydrated molecular bilayers of dilauroylphosphatidylcholine/dipalmitoylphasphatidylcholine (DLPC/DPPC) (1:1) and phosphatidylserine (PS)/DPPC (1:2) are visualized directly by low dose diffraction-contrast electron microscopy. The temperature and humidity of the bilayers are controlled by an environmental chamber set in an electron microscope. The contrast between crystalline domains is enhanced by electron optical filtering of the diffraction patterns of the bilayers. The domains are seen as a patchwork in the plane of the bilayer, with an average width of 0.2-0.5 micrometer. The percentage of solidus area measured from diffraction-contrast micrographs at various temperatures agrees in general with those depicted by known phase diagrams. The shape and size of the domains resemble those seen by freeze-fracture in multilamellar vesicles. Temperature-related changes in domain size and in phase boundary per unit area are more pronounced in the less miscible DLPC/DPPC mixture. No significant change in these geometric parameters with temperature is found in the PS/DPPC mixture. Mapping domains by their molecular diffraction signals not only verifies the existance of areas of different molecular packing during phase separation but also provides a quantitative measurement of structural boundaries and defects in lipid bilayers. Images FIGURE 1 FIGURE 3 FIGURE 6 PMID:6894707

Spatially Assembled Bilayer Cell Sheets of Stem Cells and Endothelial Cells Using Thermosensitive Hydrogels for Therapeutic Angiogenesis.

PubMed

Jun, Indong; Ahmad, Taufiq; Bak, Seongwoo; Lee, Joong-Yup; Kim, Eun Mi; Lee, Jinkyu; Lee, Yu Bin; Jeong, Hongsoo; Jeon, Hojeong; Shin, Heungsoo

2017-05-01

Although the coculture of multiple cell types has been widely employed in regenerative medicine, in vivo transplantation of cocultured cells while maintaining the hierarchical structure remains challenging. Here, a spatially assembled bilayer cell sheet of human mesenchymal stem cells and human umbilical vein endothelial cells on a thermally expandable hydrogel containing fibronectin is prepared and its effect on in vitro proangiogenic functions and in vivo ischemic injury is investigated. The expansion of hydrogels in response to a temperature change from 37 to 4 °C allows rapid harvest and delivery of the bilayer cell sheet to two different targets (an in vitro model glass surface and in vivo tissue). The in vitro study confirms that the bilayer sheet significantly increases proangiogenic functions such as the release of nitric oxide and expression of vascular endothelial cell genes. In addition, transplantation of the cell sheet from the hydrogels into a hindlimb ischemia mice model demonstrates significant retardation of necrosis particularly in the group transplated with the bilayer sheet. Collectively, the bilayer cell sheet is readily transferrable from the thermally expandable hydrogel and represents an alternative approach for recovery from ischemic injury, potentially via improved cell-cell communication. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Penetration of Gold Nanoparticles through Human Skin: Unraveling Its Mechanisms at the Molecular Scale.

PubMed

Gupta, Rakesh; Rai, Beena

2016-07-28

Recent experimental studies suggest that nanosized gold nanoparticles (AuNPs) are able to penetrate into the deeper layer (epidermis and dermis) of rat and human skin. However, the mechanisms by which these AuNPs penetrate and disrupt the skin's lipid matrix are not well understood. In this study, we have used computer simulations to explore the translocation and the permeation of AuNPs through the model skin lipid membrane using both unconstrained and constrained coarse-grained molecular dynamics simulations. Each AuNP (1-6 nm) disrupted the bilayer packing and entered the interior of the bilayer rapidly (within 100 ns). It created a hydrophobic vacancy in the bilayer, which was mostly filled by skin constituents. Bigger AuNPs induced changes in the bilayer structure, and undulations were observed in the bilayer. The bilayer exhibited self-healing properties; it retained its original form once the simulation was run further after the removal of the AuNPs. Constrained simulation results showed that there was a trade-off between the kinetics and thermodynamics of AuNP permeation at a molecular scale. The combined effect of both resulted in a high permeation of small-sized AuNPs. The molecular-level information obtained through our simulations offers a very convenient method to design novel drug delivery systems and effective cosmetics.

Nodal bilayer-splitting controlled by spin-orbit interactions in underdoped high-T c cuprates

DOE PAGES

Harrison, N.; Ramshaw, B. J.; Shekhter, A.

2015-06-03

The highest superconducting transition temperatures in the cuprates are achieved in bilayer and trilayer systems, highlighting the importance of interlayer interactions for high T c. It has been argued that interlayer hybridization vanishes along the nodal directions by way of a specific pattern of orbital overlap. Recent quantum oscillation measurements in bilayer cuprates have provided evidence for a residual bilayer-splitting at the nodes that is sufficiently small to enable magnetic breakdown tunneling at the nodes. Here we show that several key features of the experimental data can be understood in terms of weak spin-orbit interactions naturally present in bilayer systems,more » whose primary effect is to cause the magnetic breakdown to be accompanied by a spin flip. These features can now be understood to include the equidistant set of three quantum oscillation frequencies, the asymmetry of the quantum oscillation amplitudes in c-axis transport compared to ab-plane transport, and the anomalous magnetic field angle dependence of the amplitude of the side frequencies suggestive of small effective g-factors. We suggest that spin-orbit interactions in bilayer systems can further affect the structure of the nodal quasiparticle spectrum in the superconducting phase. PACS numbers: 71.45.Lr, 71.20.Ps, 71.18.+y« less

Ion-binding properties of a K+ channel selectivity filter in different conformations.

PubMed

Liu, Shian; Focke, Paul J; Matulef, Kimberly; Bian, Xuelin; Moënne-Loccoz, Pierre; Valiyaveetil, Francis I; Lockless, Steve W

2015-12-08

K(+) channels are membrane proteins that selectively conduct K(+) ions across lipid bilayers. Many voltage-gated K(+) (KV) channels contain two gates, one at the bundle crossing on the intracellular side of the membrane and another in the selectivity filter. The gate at the bundle crossing is responsible for channel opening in response to a voltage stimulus, whereas the gate at the selectivity filter is responsible for C-type inactivation. Together, these regions determine when the channel conducts ions. The K(+) channel from Streptomyces lividians (KcsA) undergoes an inactivation process that is functionally similar to KV channels, which has led to its use as a practical system to study inactivation. Crystal structures of KcsA channels with an open intracellular gate revealed a selectivity filter in a constricted conformation similar to the structure observed in closed KcsA containing only Na(+) or low [K(+)]. However, recent work using a semisynthetic channel that is unable to adopt a constricted filter but inactivates like WT channels challenges this idea. In this study, we measured the equilibrium ion-binding properties of channels with conductive, inactivated, and constricted filters using isothermal titration calorimetry (ITC). EPR spectroscopy was used to determine the state of the intracellular gate of the channel, which we found can depend on the presence or absence of a lipid bilayer. Overall, we discovered that K(+) ion binding to channels with an inactivated or conductive selectivity filter is different from K(+) ion binding to channels with a constricted filter, suggesting that the structures of these channels are different.

Supported lipid bilayer/carbon nanotube hybrids

NASA Astrophysics Data System (ADS)

Zhou, Xinjian; Moran-Mirabal, Jose M.; Craighead, Harold G.; McEuen, Paul L.

2007-03-01

Carbon nanotube transistors combine molecular-scale dimensions with excellent electronic properties, offering unique opportunities for chemical and biological sensing. Here, we form supported lipid bilayers over single-walled carbon nanotube transistors. We first study the physical properties of the nanotube/supported lipid bilayer structure using fluorescence techniques. Whereas lipid molecules can diffuse freely across the nanotube, a membrane-bound protein (tetanus toxin) sees the nanotube as a barrier. Moreover, the size of the barrier depends on the diameter of the nanotube-with larger nanotubes presenting bigger obstacles to diffusion. We then demonstrate detection of protein binding (streptavidin) to the supported lipid bilayer using the nanotube transistor as a charge sensor. This system can be used as a platform to examine the interactions of single molecules with carbon nanotubes and has many potential applications for the study of molecular recognition and other biological processes occurring at cell membranes.

Measurement of the electronic compressibility of bilayer graphene

NASA Astrophysics Data System (ADS)

Henriksen, E. A.; Eisenstein, J. P.

2010-03-01

We report on recent measurements of the electronic compressibility in bilayer graphene. The devices consist of a mechanically exfoliated bilayer graphene flake in a dual-gated configuration, having a global back gate from the underlying Si substrate and a lithographically defined top gate. With suitable shielding, an oscillating voltage applied to the back gate will generate corresponding signals in the top gate only via electric fields which penetrate the graphene, thereby allowing a direct measurement of the compressibility of the bilayer [1]. In our experiments, we map this quantity as a function of the back and top gate bias voltages and compare it to similar maps of the graphene sheet resistivity and capacitance. We discuss our results in light of numerical calculations of the underlying band structure as well as recent theoretical predictions. [1] J. P. Eisenstein, L. N. Pfeiffer, K. W. West, Phys. Rev. B 50, 1760 (1994).

Continuous planar phospholipid bilayer supported on porous silicon thin film reflector.

PubMed

Cunin, Frédérique; Milhiet, Pierre-Emmanuel; Anglin, Emily; Sailor, Michael J; Espenel, Cédric; Le Grimellec, Christian; Brunel, Daniel; Devoisselle, Jean-Marie

2007-10-01

Reconstituting artificial membranes for in vitro studies of cell barrier mechanisms and properties is of major interest in biology. Here, artificial membranes supported on porous silicon photonic crystal reflectors are prepared and investigated. The materials are of interest for label-free probing of supported membrane events such as protein binding, molecular recognition, and transport. The porous silicon substrates are prepared as multilayered films consisting of a periodically varying porosity, with pore dimensions of a few nanometers in size. Planar phospholipid bilayers are deposited on the topmost surface of the oxidized hydrophilic mesoporous silicon films. Atomic force microscopy provides evidence of continuous bilayer deposition at the surface, and optical measurements indicate that the lipids do not significantly infiltrate the porous region. The presence of the supported bilayer does not obstruct the optical spectrum from the porous silicon layer, suggesting that the composite structures can act as effective optical biosensors.

Neutron diffraction studies of amphipathic helices in phospholipid bilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bradshaw, J.P.; Gilchrist, P.J.; Duff, K.C.

The structural feature which is thought to facilitate the interaction of many peptides with phospholipid bilayers is the ability to fold into an amphipathic helix. In most cases the exact location and orientation of this helix with respect to the membrane is not known, and may vary with factors such as pH and phospholipid content of the bilayer. The growing interest in this area is stimulated by indications that similar interactions can contribute to the binding of certain hormones to their cell-surface receptors. We have been using the techniques of neutron diffraction from stacked phospholipid bilayers in an attempt tomore » investigate this phenomenon with a number of membrane-active peptides. Here we report some of our findings with three of these: the bee venom melittin; the hormone calcitonin; and a synthetic peptide representing the ion channel fragment of influenza A M2 protein.« less

Folded Optical Phonons in Twisted Bilayer Graphene: Raman Signature of Graphene Superlattices

NASA Astrophysics Data System (ADS)

Wang, Yanan; Su, Zhihua; Wu, Wei; Xing, Sirui; Lu, Xiaoxiang; Lu, Xinghua; Pei, Shin-Shem; Robles-Hernandez, Francisco; Hadjiev, Viktor; Bao, Jiming

2013-03-01

In contrast to Bernal-stacked graphene exfoliated from HOPG, twisted bilayer graphene are widely observed in the samples prepared by silicon sublimation of SiC or chemical vapor deposition (CVD). However, many of its basic properties still remain unrevealed. In this work, hexagon-shaped bilayer graphene islands synthesized by CVD method were systematically studied using Raman spectroscopy. A series of folded phonons were observed in the range from 1375 cm-1 to 1525 cm-1. The frequency of folded phonon modes doesn't shift with laser excitation energy, but it is highly dependent on the rotational angle between two layers. In general, the frequency of folded phonon decreases with the increase of rotation angle. This rotation dependence can be qualitatively explained by the folding of phonon dispersion curve of single layer graphene into the reduced Brillouin zone of bilayer superlattice. The obseravtion of folded phonon is an important indication of superlattice band structure.

Biomimetic membrane arrays on cast hydrogel supports.

PubMed

Roerdink Lander, Monique; Ibragimova, Sania; Rein, Christian; Vogel, Jörg; Stibius, Karin; Geschke, Oliver; Perry, Mark; Hélix-Nielsen, Claus

2011-06-07

Lipid bilayers are intrinsically fragile and require mechanical support in technical applications based on biomimetic membranes. Tethering the lipid bilayer membranes to solid substrates, either directly through covalent or ionic substrate-lipid links or indirectly on substrate-supported cushions, provides mechanical support but at the cost of small molecule transport through the membrane-support sandwich. To stabilize biomimetic membranes while allowing transport through a membrane-support sandwich, we have investigated the feasibility of using an ethylene tetrafluoroethylene (ETFE)/hydrogel sandwich as the support. The sandwich is realized as a perforated surface-treated ETFE film onto which a hydrogel composite support structure is cast. We report a simple method to prepare arrays of lipid bilayer membranes with low intrinsic electrical conductance on the highly permeable, self-supporting ETFE/hydrogel sandwiches. We demonstrate how the ETFE/hydrogel sandwich support promotes rapid self-thinning of lipid bilayers suitable for hosting membrane-spanning proteins.

Lipid-bilayer-assisted two-dimensional self-assembly of DNA origami nanostructures

NASA Astrophysics Data System (ADS)

Suzuki, Yuki; Endo, Masayuki; Sugiyama, Hiroshi

2015-08-01

Self-assembly is a ubiquitous approach to the design and fabrication of novel supermolecular architectures. Here we report a strategy termed `lipid-bilayer-assisted self-assembly' that is used to assemble DNA origami nanostructures into two-dimensional lattices. DNA origami structures are electrostatically adsorbed onto a mica-supported zwitterionic lipid bilayer in the presence of divalent cations. We demonstrate that the bilayer-adsorbed origami units are mobile on the surface and self-assembled into large micrometre-sized lattices in their lateral dimensions. Using high-speed atomic force microscopy imaging, a variety of dynamic processes involved in the formation of the lattice, such as fusion, reorganization and defect filling, are successfully visualized. The surface modifiability of the assembled lattice is also demonstrated by in situ decoration with streptavidin molecules. Our approach provides a new strategy for preparing versatile scaffolds for nanofabrication and paves the way for organizing functional nanodevices in a micrometer space.