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Sample records for gel-phase dppc bilayers

  1. Effects of cholesterol on phospholipid membranes: inhibition of the interdigitated gel phase of F-DPPC and F-DPPC/DPPC.

    Science.gov (United States)

    Smith, Eric A; Wang, Weidong; Dea, Phoebe K

    2012-02-01

    Unlike the parent phospholipid, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), the monofluorinated analog, 1-palmitoyl-2-(16-fluoropalmitoyl)sn-glycero-3-phosphocholine (F-DPPC), spontaneously forms an interdigitated gel phase (L(β)I) below the main transition temperature (T(m)). We have examined the effects of introducing cholesterol to F-DPPC and 1:1 F-DPPC/DPPC membranes using a combination of DSC, optical density, fluorescence intensity and polarization, (31)P NMR, and X-ray diffraction techniques. Cholesterol increases the fluidity of the gel phase, broadens the main transition, and decreases the main transition enthalpy. However, these results also reveal that there is an unusually large degree of phase coexistence between the L(β)I and non-interdigitated gel phases when cholesterol is added. Cholesterol encourages this phase segregation by partitioning into the thicker non-interdigitated domains. At higher cholesterol concentrations, the majority or all of the L(β)I phase of F-DPPC and 1:1 F-DPPC/DPPC is eliminated and is replaced by a non-interdigitated liquid-ordered (l(o)) phase with properties similar to DPPC/cholesterol. Consequently, cholesterol mitigates the influence the CF moiety has on the thermodynamic phase behavior of F-DPPC. Our findings demonstrate that there are multiple characteristics of cholesterol-rich membranes that disfavor interdigitation.

  2. The effect of temperature on supported dipalmitoylphosphatidylcholine (DPPC) bilayers: structure and lubrication performance.

    Science.gov (United States)

    Wang, Min; Zander, Thomas; Liu, Xiaoyan; Liu, Chao; Raj, Akanksha; Wieland, D C Florian; Garamus, Vasil M; Willumeit-Römer, Regine; Claesson, Per Martin; Dėdinaitė, Andra

    2015-05-01

    Phospholipids fulfill an important role in joint lubrication. They, together with hyaluronan and glycoproteins, are the biolubricants that sustain low friction between cartilage surfaces bathed in synovial fluid. In this work we have investigated how the friction force and load bearing capacity of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) bilayers on silica surfaces are affected by temperature, covering the temperature range 25-52°C. Friction forces have been determined utilizing the AFM colloidal probe technique, which showed that DPPC bilayers are able to provide low friction forces over the whole temperature interval. However, the load bearing capacity is improved at higher temperatures. We interpret this finding as being a consequence of lower rigidity and higher self-healing capacity of the DPPC bilayer in the liquid disordered state compared to the gel state. The corresponding structure of solid supported DPPC bilayers at the silica-liquid interface has been followed using X-ray reflectivity measurements, which suggests that the DPPC bilayer is in the gel phase at 25°C and 39°C and in the liquid disordered state at 55°C. Well-defined bilayer structures were observed for both phases. The deposited DPPC bilayers were also imaged using AFM PeakForce Tapping mode, and these measurements indicated a less homogeneous layer at temperatures below 37°C.

  3. Low concentration of DMSO stabilizes the bilayer gel phase rather than the interdigitated gel phase in dihexadecylphosphatidylcholine membrane.

    Science.gov (United States)

    Yamashita, Y; Kinoshita, K; Yamazaki, M

    2000-08-25

    We have investigated effects of dimethylsulfoxide (DMSO) on the phase stability of multilamellar vesicles of the ether-linked 1,2-dihexadecyl-sn-glycero-3-phosphatidylcholine (DHPC-MLV), which is known to be in the interdigitated gel (LbetaI) phase in excess water at 20 degrees C. The results of X-ray diffraction experiments indicate that the DHPC membrane was in the Lbeta, phase at X> or =0.12 (X=mole fraction of DMSO in DMSO/water mixture). The result of differential scanning calorimetry indicate that the gel to liquid-crystalline phase transition temperature increased, but the LbetaI to Pbeta, phase transition temperature decreased with an increase in DMSO concentration. These results show that DMSO stabilizes the bilayer gel phase rather than the LbetaI phase at its low concentration. The solubility of phosphorylcholine, which is the same structure as the headgroup of DHPC, decreased with an increase in DMSO concentration, indicating that the interaction free energy of the hydrophilic segments of the membrane with solvents increases with an increase in DMSO concentration. On the basis of the thermodynamic analysis, the mechanism of the stabilization of the bilayer gel phase of DHPC-MLV by DMSO is discussed. The decrease in the repulsive interaction between the headgroups of the phospholipid induced by the low concentrations of DMSO in water plays an important role in this stabilization.

  4. Interaction of S-methyl methanethiosulfonate with DPPC bilayer

    Science.gov (United States)

    Defonsi Lestard, María E.; Díaz, Sonia B.; Tuttolomondo, María E.; Sánchez Cortez, Santiago; Puiatti, Marcelo; Pierini, Adriana B.; Ben Altabef, Aida

    2012-11-01

    The present study is a first step towards the investigation of S-methyl methanethiosulfonate (MMTS) interaction with membrane model systems like liposomes. In this paper, the interaction of MMTS with dipalmitoylphosphatidylcholine (DPPC) bilayers was studied by FTIR and SERS spectroscopy. Lysolipid effect on vesicle stability was studied. The results show that MMTS interacts to different extents with the phosphate and carbonyl groups of membranes in the gel and the liquid crystalline states. To gain a deeper insight into MMTS properties that may be potentially helpful in the design of new drugs with therapeutic effects, we performed theoretical studies that may be the basis for the design of their mode of action.

  5. Molecular dynamics simulations and free energy profile of Paracetamol in DPPC and DMPC lipid bilayers

    Indian Academy of Sciences (India)

    Yousef Nademi; Sepideh Amjad Iranagh; Abbas Yousefpour; Seyedeh Zahra Mousavi; Hamid Modarress

    2014-05-01

    Molecular dynamics (MD) simulations and biased MD simulation were carried out for the neutral form of Paracetamol inserted in fully hydrated dipalmitoylphosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) lipid bilayers. For comparison, fully hydrated DMPC and DPPC lipid bilayers were also simulated separately without Paracetamol. The simulation time for each system was 50 ns. At two concentrations of Paracetamol, various properties of the lipid bilayer such as area per lipid, order parameter, diffusion coefficient, radial distribution function, electrostatic potential, mass density and hydrogen bonds have been calculated. Also, the convergence in time of the free energy profile of the Paracetamol along a DPPC bilayer normal was calculated by umbrella sampling method. From the obtained results, it can be concluded that neutral form of Paracetamol shows a generally similar behaviour in DPPC and DMPC lipid bilayers. It was shown that the addition of Paracetamol causes a decrease in tail order parameter of both DPPC and DMPC lipid bilayers and the tail of Paracetamol adopts an inward orientation in the lipid bilayers. Also from the free energy profile, the high penetration barrier in the bilayer centre was determined.

  6. Cholesterol effect on water permeability through DPPC and PSM lipid bilayers: a molecular dynamics study.

    Science.gov (United States)

    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.

  7. Structure and phase transformations of DPPC lipid bilayers in the presence of nanoparticles: insights from coarse-grained molecular dynamics simulations.

    Science.gov (United States)

    Prates Ramalho, J P; Gkeka, P; Sarkisov, L

    2011-04-05

    In this article, we investigate fluid-gel transformations of a DPPC lipid bilayer in the presence of nanoparticles, using coarse-grained molecular dynamics. Two types of nanoparticles are considered, specifically a 3 nm hydrophobic nanoparticle located in the core of the bilayer and a 6 nm charged nanoparticle located at the interface between the bilayer and water phase. Both negatively and positively charged nanoparticles at the bilayer interface are investigated. We demonstrate that the presence of all types of nanoparticles induces disorder effects in the structure of the lipid bilayer. These effects are characterized using computer visualization of the gel phase in the presence of nanoparticles, radial distribution functions, and order parameters. The 3 nm hydrophobic nanoparticle immersed in the bilayer core and the positively charged nanoparticle at the bilayer surface have no effect on the temperature of the fluid-gel transformation, compared to the bulk case. Interestingly, a negatively charged hydrophobic nanoparticle located at the surface of the bilayer causes slight shift of the fluid-gel transformation to a lower temperature, compared to the bulk bilayer case.

  8. Low pH induces an interdigitated gel to bilayer gel phase transition in dihexadecylphosphatidylcholine membrane.

    Science.gov (United States)

    Furuike, S; Levadny, V G; Li, S J; Yamazaki, M

    1999-10-01

    We have investigated the influence of pH on the structures and phase behaviors of multilamellar vesicles of the ether-linked dihexadecylphosphatidylcholine (DHPC-MLV). This phospholipid is known to be in the interdigitated gel (L(beta)I) phase in excess water at 20 degrees C at neutral pH. The results of X-ray diffraction experiments indicate that a phase transition from L(beta)I phase to the bilayer gel phase occurred in DHPC-MLV in 0.5 M KCl around pH 3.9 with a decrease in pH, and that at low pH values, less than pH 2.2, DHPC-MLVs were in L(beta') phase. The results of fluorescence and light scattering method indicate that the gel to liquid-crystalline phase transition temperature (T(m)) of DHPC-MLV increased with a decrease in pH. On the basis of a thermodynamic analysis, we conclude that the main mechanism of the low-pH induced L(beta)I to bilayer gel phase transition in DHPC-MLV and the increase in its T(m) is connected with the decrease in the repulsive interaction between the headgroups of these phospholipids. As pH decreases, the phosphate groups of the headgroups begin to be protonated, and as a result, the apparent positive surface charges appear. However, surface dipoles decrease and the interaction free energy of the hydrophilic segments with water increases. The latter effect dominates the pure electrostatic repulsion between the charged headgroups, and thereby, the total repulsive interaction in the interface decreases.

  9. ATR-IR spectroscopic study of the structural changes in the hydrophobic region of ICPAN/DPPC bilayers

    Science.gov (United States)

    Cieślik-Boczula, Katarzyna; Czarnik-Matusewicz, Bogusława; Perevozkina, Margarita; Filarowski, Aleksander; Boens, Noël; De Borggraeve, Wim M.; Koll, Aleksander

    2008-04-01

    Structural changes in the hydrophobic region in the self-aggregates of the long hydrocarbon chain ICPAN ((( N, N-dimethyl- N-octyl-2-ammonioethyl)-3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate bromide)) homologues and their interaction with a DPPC (dipalmitoylophosphatidylcholine) bilayer were the subject of detailed investigation using ATR infrared spectroscopy. On the base of analysis of the bands assigned to CH 2 stretching, scissoring, and rocking and CH wagging vibrations it was revealed that the hydrophobic parts ICPANs adopt a gauche-rich disordering structure. Moreover, it was shown that the micellar- or lamellar-like character of these structures depends on the hydrocarbon chain length. Results obtained from the ICPAN/DPPC mixtures indicate an increase in the conformational disorder in hydrophobic part compare to pure DPPC film. This effect depends on the length of the aliphatic chain of ICPAN homologues and on the relative concentrations of DPPC and ICPAN.

  10. [Study on the Effects of Ginsenoside Rb1 on DPPC Bilayers by Using Thermo-Raman Spectrum and DSC].

    Science.gov (United States)

    Hui, Ge; Liu, Wei; Zhang, Jing-zhou; Zhou, Tie-li; Wang, Si-ming; Zhao, Yu; Zhao, Bing

    2015-08-01

    The research on the interactions between Ginsenosides and biomembranes plays a crucial role in thorough understanding the pharmacological activity and biologyical effect of Chinese medicine Panax ginseng. With the bilayer structure, DPPC often serves as an simulation model of the cell membrane to study the role of drug molecules and cell membranes. Ginsenoside Rb1, one of the most important components of Panaxginseng, playing the significant roles of pharmacological effects and biological properties. Raman and differential scanning calorimetry (DSC) are respectively a powerful tool for discussing the molecular interaction, and a kind of general technology by which researching the bilayer monomer structures and its interactions with drug molecules. However, rarely research reports on the interactions between drug molecules and biomembranes by means of both technologies above. In this paper, the influence of ginsenoside monomer Rb1 on DPPC membrane bilayers was investigated by thermo-Raman and DSC. In Raman spectra, the changes of DPPC molecule have been observed before and after interacted with ginsenoside Rb1, the data analysis indicates three aspects: the O-C-C-N+ polar head group skeleton, C-C stretching vibration area, and the C-H bond stretching vibrarion in terminated methyl group of alkyl chains. The results showed that ginsenoside Rb1 molecule with certain concentration has not changed the gauche conformation of the polar head backbone group in DPPC bilayers, the order of the internal molecular chain and the lateral chain-chain packing have been decreased as the temperature increased, the lateral disposed disorder has been increased. The changes of some thermodynamic constants obtained by DSC experiment such as phase transition temperature (Tm), the temperature at which the transition is half completed (ΔT1/2), and the transition enthalpy normalized per mol of DPPC (AH) have been showed further results of the thermo Raman experiments, with increasing the

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

    Science.gov (United States)

    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.

  12. Lipid Bilayers in the Gel Phase Become Saturated by Triton X-100 at Lower Surfactant Concentrations Than Those in the Fluid Phase

    Science.gov (United States)

    Ahyayauch, Hasna; Collado, M. Isabel; Alonso, Alicia; Goñi, Felix M.

    2012-01-01

    It has been repeatedly observed that lipid bilayers in the gel phase are solubilized by lower concentrations of Triton X-100, at least within certain temperature ranges, or other nonionic detergents than bilayers in the fluid phase. In a previous study, we showed that detergent partition coefficients into the lipid bilayer were the same for the gel and the fluid phases. In this contribution, turbidity, calorimetry, and 31P-NMR concur in showing that bilayers in the gel state (at least down to 13–20°C below the gel-fluid transition temperature) become saturated with detergent at lower detergent concentrations than those in the fluid state, irrespective of temperature. The different saturation may explain the observed differences in solubilization. PMID:22713566

  13. Resveratrol induces chain interdigitation in DPPC cell membrane model systems.

    Science.gov (United States)

    Longo, Elena; Ciuchi, Federica; Guzzi, Rita; Rizzuti, Bruno; Bartucci, Rosa

    2016-12-01

    Resveratrol is a natural polyphenol found in various plants with potential therapeutic activity as anti-oxidant, anti-inflammatory, cardioprotective and anti-tumoral. Lipid membranes are among cellular components that are targets of its action. In this work ESR of chain labeled lipids, calorimetry, X-ray diffraction and molecular docking are used to study the interaction of resveratrol with membrane model systems of dipalmitoylphosphatidylcholine (DPPC) as a function of resveratrol concentration (0-30 mol% of the lipid) and temperature (10-50°C). Resveratrol incorporated in DPPC bilayers induces considerable motional restriction at the lipid tail termini, removing the gradient of increasing mobility along the chain found in DPPC bilayers in the gel phase. In contrast, it leaves unperturbed the DPPC chain flexibility profile in the liquid-crystalline phase. At low concentration, resveratrol progressively reduces the pre-transition temperature and eliminates the pre-transition for content ≥5mol%. A reduced cooperativity and a downshift of the main transition temperature are observed, especially at high content. The typical diffraction pattern of DPPC multibilayers in the Lβ' phase is converted to a lamellar pattern with reduced d-spacing of untilted lipid chain in a hexagonal packing at 30 mol% of resveratrol. Molecular docking indicates that the energetically favoured anchoring site is the polar headgroup region, where resveratrol acts as a spacer. The overall results are consistent with the formation in DPPC of an interdigitated Lβi gel phase induced by 30 mol% resveratrol. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Molecular dynamics simulation of human serum paraoxonase 1 in DPPC bilayer reveals a critical role of transmembrane helix H1 for HDL association.

    Science.gov (United States)

    Patra, Mahesh Chandra; Rath, Surya Narayan; Pradhan, Sukanta Kumar; Maharana, Jitendra; De, Sachinandan

    2014-01-01

    Serum paraoxonase 1 (PON1) is a high-density lipoprotein (HDL)-bound mammalian enzyme exhibiting antiatherosclerotic activity. Despite years of research, an accurate model for the binding interaction between PON1 and HDL has not been established. However, it is reported that anchoring of PON1 to HDL is mainly governed by an N-terminal alpha helix H1 and another short helix H2. Here, we studied the molecular association of full-length human PON1 (huPON1) with a HDL-mimetic dipalmitoylphosphatidylcholine (DPPC) bilayer using homology modeling and molecular dynamics simulations. Our results indicate that H1 is the highly dynamic part of huPON1, showing clockwise rotation of up to 30° within the DPPC bilayer. However, without phospholipid molecules, H1 experiences helical distortions, illustrating an incompatible HDL-anchoring conformation. Snorkeling interactions of K3, R18, and R27 together with aromatic locks formed by Y187, Y190, W194, and W202 are highly essential for anchoring of huPON1 to HDL's surface. Molecular mechanics/Poisson-Boltzmann solvent-accessible surface area (MM/PBSA) binding free energy calculation revealed that H1 displays greater binding affinity towards lipid molecules compared with H2 and H3, suggesting that H1 is the most probable HDL-binding domain of PON1. Binding free energy decomposition showed that K3, R18, and R27 interact with polar headgroups of DPPC membrane through electrostatic interaction. Moreover, Y187, Y190, W194, and W202 interact with DPPC lipids mainly through van der Waals interaction. Taken together, these results show that the transmembrane helix H1 along with the interfacial positively charged and aromatic resides were crucial for PON1's association with HDL particle. The current study will be useful towards understanding the antiatherosclerotic and bioscavenging properties of this promiscuous enzyme.

  15. Lipid reassembly in asymmetric Langmuir-Blodgett/Langmuir-Schaeffer bilayers.

    Science.gov (United States)

    Yuan, Jie; Hao, Changchun; Chen, Maohui; Berini, Pierre; Zou, Shan

    2013-01-08

    Molecular-reorganization-induced morphology alteration in asymmetric substrate-supported lipid bilayers (SLBs) was directly visualized by means of atomic force microscopy (AFM) and total internal reflection fluorescence (TIRF) microscopy. SLB samples were fabricated on mica-on-glass and glass substrates by Langmuir-Blodgett (LB)/Langmuir-Schaeffer (LS) using binary lipid mixtures, namely, 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC)/1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and ternary mixtures DOPC/DPPC/1,2-dioleoyl-sn-glycero-3-phospho-L-serine (DOPS), labeled with 0.2 mol % Texas Red 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine triethylammonium salt (TR-DHPE) dye. Phase segregations were characterized by TIRF imaging, and DPPC-enriched domain structures were also observed. Interestingly for ∼40% (n = 6) of the samples with binary mixtures in the LB leaflet and a single component in the LS leaflet, that is, (DOPC/DPPC)(LB)+DOPC(LS), the contrast of the DPPC domains changed from the original dark (without dye) to bright (more TR dye partitioning) on TIRF images, returning to dark again. This contrast reverse was also correlated to AFM height images, where a DPPC-DPPC gel phase was spotted after the TIRF image contrast returned to dark. The rupture force mapping results measured on these binary mixture samples also confirmed unambiguously the formation of DPPC-DPPC gel domain components during the contrast change. The samples were tracked over 48 h to investigate the lipid molecule movements in both the DPPC domains and the DOPC fluid phase. The fluorescence contrast changes from bright to dark in SLBs indicate that the movement of dye molecules was independent of the movement of lipid molecules. In addition, correlated multimodal imaging using AFM, force mapping, and fluorescence provides a novel route to uncover the reorganization of lipid molecules at the solid-liquid interface, suggesting that the dynamics of dye molecules is highly

  16. Hydrophobic silver nanoparticles trapped in lipid bilayers: Size distribution, bilayer phase behavior, and optical properties

    Directory of Open Access Journals (Sweden)

    Bothun Geoffrey D

    2008-11-01

    Full Text Available Abstract Background Lipid-based dispersion of nanoparticles provides a biologically inspired route to designing therapeutic agents and a means of reducing nanoparticle toxicity. Little is currently known on how the presence of nanoparticles influences lipid vesicle stability and bilayer phase behavior. In this work, the formation of aqueous lipid/nanoparticle assemblies (LNAs consisting of hydrophobic silver-decanethiol particles (5.7 ± 1.8 nm embedded within 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC bilayers is demonstrated as a function of the DPPC/Ag nanoparticle (AgNP ratio. The effect of nanoparticle loading on the size distribution, bilayer phase behavior, and bilayer fluidity is determined. Concomitantly, the effect of bilayer incorporation on the optical properties of the AgNPs is also examined. Results The dispersions were stable at 50°C where the bilayers existed in a liquid crystalline state, but phase separated at 25°C where the bilayers were in a gel state, consistent with vesicle aggregation below the lipid melting temperature. Formation of bilayer-embedded nanoparticles was confirmed by differential scanning calorimetry and fluorescence anisotropy, where increasing nanoparticle concentration suppressed the lipid pretransition temperature, reduced the melting temperature, and disrupted gel phase bilayers. The characteristic surface plasmon resonance (SPR wavelength of the embedded nanoparticles was independent of the bilayer phase; however, the SPR absorbance was dependent on vesicle aggregation. Conclusion These results suggest that lipid bilayers can distort to accommodate large hydrophobic nanoparticles, relative to the thickness of the bilayer, and may provide insight into nanoparticle/biomembrane interactions and the design of multifunctional liposomal carriers.

  17. Influence of the interdigitated gel phase in mixtures of ether-linked and monofluorinated ester-linked phospholipids.

    Science.gov (United States)

    Smith, Eric A; Dea, Phoebe K

    2012-12-01

    To evaluate the influence of the hydrocarbon chain linkage on the thermodynamic phase behavior of spontaneously interdigitating lipids, mixtures of ether-linked 1,2-di-O-hexadecyl-phosphocholine (DHPC) and ester-linked 1-palmitoyl-2-[16-fluoropalmitoyl]sn-glycero-3-phosphocholine (F-DPPC) were studied. A combination of differential scanning calorimetry (DSC), fluorescence spectroscopy, and transmittance spectrophotometry was used. Small amounts of F-DPPC increase the pretransition temperature (T(p)) between the interdigitated gel phase (L(β)I) and the ripple gel phase (P(β)'). There are some signs of immiscibility where the non-interdigitated lipid is present in the phase diagram. However, at around 20mol.% F-DPPC, the pretransition merges with the main transition and is no longer detectable as a separate entity. Additionally, the T(m) hysteresis increases steadily with higher mole fractions of F-DPPC. These results support that incorporating F-DPPC progressively stabilizes the L(β)I phase of DHPC until the membrane is fully interdigitated below the main transition temperature (T(m)). The mixtures of F-DPPC and DHPC are miscible once the membrane is entirely interdigitated in the gel phase. Therefore, the ability of both lipids to interdigitate is an important factor controlling gel phase miscibility. Our results also demonstrate that the gel phase behavior of DHPC is highly sensitive to changes in its environment.

  18. Bilayer characteristics of a diether phosphonolipid analog of the major lung surfactant glycerophospholipid dipalmitoyl phosphatidylcholine.

    Science.gov (United States)

    Skita, V; Chester, D W; Oliver, C J; Turcotte, J G; Notter, R H

    1995-05-01

    Thermal and lyotropic phase behavior was studied by X-ray diffraction and differential scanning calorimetry for a diether phosphonolipid analog (DEPN-8) of the major lung surfactant glycerophospholipid dipalmitoyl phosphatidylcholine (DPPC). DEPN-8 differs in an ether, rather than an ester, bond at the acyl chain-backbone linkage and a headgroup phosphonate (isosteric methylene substitution) versus phosphate constituent. Analysis of lamellar diffraction maxima demonstrated that at high relative humidity (98%) and temperatures below the liquid crystal phase transition (approximately 45 degrees C), DEPN-8 formed interdigitated bilayers with a characteristic periodicity of 41.9-46.5 A. At low humidity the gel phase DEPN-8 bilayers were characteristic of a normal L beta phase with a periodicity equivalent to DPPC (57-59 A). Above the liquid crystal thermal phase transition, bilayer spacing for both DEPN-8 and DPPC was 51-52 A, characteristic of the L alpha phase. Complete assessments of both lamellar and in-plane X-ray scattering used to construct electron density profiles and structure-factor plots for DEPN-8 defined more fully the interdigitated bilayer state at high humidity and low temperature. Compared to DPPC, it is energetically favorable for DEPN-8 to form interdigitated bilayers under conditions of excess water and low temperature. The flexible character of the ether bonds in DEPN-8 allows increased hydrophobic interactions between acyl chains, without generating a steric penalty from the increased packing density of the molecules. Additionally, the ether bond and the phosphonate moiety may allow for more energetically favorable interactions between the choline portion of the headgroup and water. The DEPN-8 ether linkage may also contribute to the improved adsorption and film respreading found previously for this phosphonolipid compared to DPPC.

  19. Ether- versus ester-linked phospholipid bilayers containing either linear or branched apolar chains.

    Science.gov (United States)

    Balleza, Daniel; Garcia-Arribas, Aritz B; Sot, Jesús; Ruiz-Mirazo, Kepa; Goñi, Félix M

    2014-09-16

    We studied the properties of bilayers formed by ether-and ester-containing phospholipids, whose hydrocarbon chains can be either linear or branched, using sn-1,2 dipalmitoyl, dihexadecyl, diphytanoyl, and diphytanyl phosphatidylcholines (DPPC, DHPC, DPhoPC, and DPhPC, respectively) either pure or in binary mixtures. Differential scanning calorimetry and confocal fluorescence microscopy of giant unilamellar vesicles concurred in showing that equimolar mixtures of linear and branched lipids gave rise to gel/fluid phase coexistence at room temperature. Mixtures containing DHPC evolved in time (0.5 h) from initial reticulated domains to extended solid ones when an equilibrium was achieved. The nanomechanical properties of supported planar bilayers formed by each of the four lipids studied by atomic force microscopy revealed average breakdown forces Fb decreasing in the order DHPC ≥ DPPC > DPhoPC > DPhPC. Moreover, except for DPPC, two different Fb values were found for each lipid. Atomic force microscopy imaging of DHPC was peculiar in showing two coexisting phases of different heights, probably corresponding to an interdigitated gel phase that gradually transformed, over a period of 0.5 h, into a regular tilted gel phase. Permeability to nonelectrolytes showed that linear-chain phospholipids allowed a higher rate of solute + water diffusion than branched-chain phospholipids, yet the former supported a smaller extent of swelling of the corresponding vesicles. Ether or ester bonds appeared to have only a minor effect on permeability.

  20. Packing characteristics of two-component bilayers composed of ester- and ether-linked phospholipids.

    Science.gov (United States)

    Batenjany, M M; O'Leary, T J; Levin, I W; Mason, J T

    1997-01-01

    The miscibility properties of ether- and ester-linked phospholipids in two-component, fully hydrated bilayers have been studied by differential scanning calorimetry (DSC) and Raman spectroscopy. Mixtures of 1,2-di-O-hexadecyl-rac-glycero-3-phosphocholine (DHPC) with 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DHPE) and of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) with 1,2-di-O-hexadecyl-sn-glycero-3-phosphoethanolamine (DHPE) have been investigated. The phase diagram for the DPPC/DHPE mixtures indicates that these two phospholipids are miscible in all proportions in the nonrippled bilayer gel phase. In contrast, the DHPC/DPPE mixtures display two regions of gel phase immiscibility between 10 and 30 mol% DPPE. Raman spectroscopic measurements of DHPC/DPPE mixtures in the C-H stretching mode region suggest that this immiscibility arises from the formation of DHPC-rich interdigitated gel phase domains with strong lateral chain packing interactions at temperatures below 27 degrees C. However, in the absence of interdigitation, our findings, and those of others, lead to the conclusion that the miscibility properties of mixtures of ether- and ester-linked phospholipids are determined by the nature of the phospholipid headgroups and are independent of the character of the hydrocarbon chain linkages. Thus it seems unlikely that the ether linkage has any significant effect on the miscibility properties of phospholipids in biological membranes. PMID:9083673

  1. Kinetics of degradation of dipalmitoylphosphatidylcholine (DPPC) bilayers as a result of vipoxin phospholipase A2 activity: an atomic force microscopy (AFM) approach

    DEFF Research Database (Denmark)

    Balashev, Konstantin; Atanasov, Vasil; Mitewa, Mariana

    2011-01-01

    the occurrence and the growth rate of the bilayer defects. The special resolution of the AFM images allowed us to measure the area and the perimeter length of these defects and to draw conclusions about the kinetics of the enzyme reaction. Moreover, we also report for some unique characteristics discovered...... the volume of these crystals and we found that their growth rate follows a similar kinetic pattern as the degradation rate of the supported bilayer....

  2. Effect of pressure on bilayer phase behavior of N-methylated di-O-hexadecylphosphatidylethanolamines: relevance of head-group modification on the bilayer interdigitation.

    Science.gov (United States)

    Goto, Masaki; Aoki, Yuya; Tamai, Nobutake; Matsuki, Hitoshi

    2017-03-30

    The phase transitions of N-methylated di-O-hexadecylphosphatidylethanolamines (DHPE, DH-N-methyl-PE (DHMePE) and DH-N,N-dimethyl-PE (DHMe2PE)) were observed by differential scanning calorimetry (DSC) and fluorometry under atmospheric pressure and by light-transmittance measurements under high pressure. The DSC thermograms showed that the N-methylated DHPE bilayers underwent the phase transition from the gel phase to the liquid crystalline (Lα) phase under atmospheric pressure. The gel phase was identified by fluorometry as the lamellar gel (Lβ) phase, and not interdigitated gel (LβI) phase. The gel/Lα transition temperature increased with pressure while decreased stepwise with increasing polar head-group size. This stepwise depression of the transition temperature may be caused by the inverse-proportional hydrogen-bonding capabilities of the head-group to the head-group size. The thermodynamic quantities of the gel/Lα transition were comparable for the N-methylated DHPE bilayers. The pressure-induced LβI phase was not found in these bilayers although the bilayer of di-O-hexadecylphosphatidylcholine (DHPC), which is a kind of N-methylated DHPEs, forms the LβI phase only by hydration under atmospheric pressure. Taking into account that the bilayers of diacyl-homologs of N-methylated DHPEs, N-methylated dipalmitoyl-PEs except for dipalmitoylphosphatidylcholine (DPPC), do not form the LβI phase in the whole pressure range investigated but the DPPC bilayer forms the LβI phase under high pressure, we can say that the interdigitation requires weaker interaction between large-sized head groups like the bulky choline group. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. The interdigitated gel phase in mixtures of cationic and zwitterionic phospholipids.

    Science.gov (United States)

    Smith, Eric A; Dea, Phoebe K

    2015-01-01

    To examine the phase behavior of mixtures of zwitterionic and cationic lipids we used three derivatives of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). All three lipids are uniquely capable of spontaneously forming the interdigitated gel phase (LβI) under typical hydration conditions. The P-O-ethyl derivative, 1,2-dipalmitoyl-sn-glycero-3-ethylphosphocholine (EDPPC), was chosen as the cationic lipid. For the zwitterionic lipids, we use the ether-linked 1,2-di-O-hexadecyl-sn-glycero-3-phosphocholine, (DHPC) and the fluorine substituted 1-palmitoyl-2-(16-fluoropalmitoyl)-sn-glycero-3-phosphocholine (F-DPPC). Differential scanning calorimetry (DSC) and fluorescence spectroscopy were used to analyze the lipid mixtures. The F-DPPC/EDPPC mixtures are interdigitated at all lipid ratios below the main transition temperature (Tm). In addition, EDPPC stabilizes the interdigitated gel phase of DHPC until the ripple gel phase (Pβ') is eliminated and only the LβI to liquid crystalline phase (Lα) main transition remains. These results demonstrate that mixtures of cationic and zwitterionic lipids can be compatible with the interdigitated phase.

  4. Phase equilibria in DOPC/DPPC: Conversion from gel to subgel in two component mixtures.

    Science.gov (United States)

    Schmidt, Miranda L; Ziani, Latifa; Boudreau, Michelle; Davis, James H

    2009-11-07

    Biological membranes contain a mixture of phospholipids with varying degrees of hydrocarbon chain unsaturation. Mixtures of long chain saturated and unsaturated lipids with cholesterol have attracted a lot of attention because of the formation of two coexisting fluid bilayer phases in such systems over a broad range of temperature and composition. Interpretation of the phase behavior of such ternary mixtures must be based on a thorough understanding of the phase behavior of the binary mixtures formed with the same components. This article describes the phase behavior of mixtures of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) with 1,2-di-d(31)-palmitoyl-sn-glycero-3-phosphocholine (DPPC) between -20 and 50 degrees C. Particular attention has been paid to the phase coexistence below about 16 degrees C where the subgel phase appears. The changes in the shape of the spectrum (and its spectral moments) during the slow transformation process leads to the conclusion that below 16 degrees C the gel phase is metastable and the gel component of the two-phase mixture slowly transforms to the subgel phase with a slightly different composition. This results in a line of three-phase coexistence near 16 degrees C. Analysis of the transformation of the metastable gel domains into the subgel phase using the nucleation and growth model shows that the subgel domain growth is a two dimensional process.

  5. Rationalization of reduced penetration of drugs through ceramide gel phase membrane.

    Science.gov (United States)

    Paloncýová, Markéta; DeVane, Russell H; Murch, Bruce P; Berka, Karel; Otyepka, Michal

    2014-11-25

    Since computing resources have advanced enough to allow routine molecular simulation studies of drug molecules interacting with biologically relevant membranes, a considerable amount of work has been carried out with fluid phospholipid systems. However, there is very little work in the literature on drug interactions with gel phase lipids. This poses a significant limitation for understanding permeation through the stratum corneum where the primary pathway is expected to be through a highly ordered lipid matrix. To address this point, we analyzed the interactions of p-aminobenzoic acid (PABA) and its ethyl (benzocaine) and butyl (butamben) esters with two membrane bilayers, which differ in their fluidity at ambient conditions. We considered a dioleoylphosphatidylcholine (DOPC) bilayer in a fluid state and a ceramide 2 (CER2, ceramide NS) bilayer in a gel phase. We carried out unbiased (100 ns long) and biased z-constraint molecular dynamics simulations and calculated the free energy profiles of all molecules along the bilayer normal. The free energy profiles converged significantly slower for the gel phase. While the compounds have comparable affinities for both membranes, they exhibit penetration barriers almost 3 times higher in the gel phase CER2 bilayer. This elevated barrier and slower diffusion in the CER2 bilayer, which are caused by the high ordering of CER2 lipid chains, explain the low permeability of the gel phase membranes. We also compared the free energy profiles from MD simulations with those obtained from COSMOmic. This method provided the same trends in behavior for the guest molecules in both bilayers; however, the penetration barriers calculated by COSMOmic did not differ between membranes. In conclusion, we show how membrane fluid properties affect the interaction of drug-like molecules with membranes.

  6. Gel-gel phase separation within milk sphingomyelin domains revealed at the nanoscale using atomic force microscopy.

    Science.gov (United States)

    Guyomarc'h, Fanny; Chen, Maohui; Et-Thakafy, Oumaima; Zou, Shan; Lopez, Christelle

    2017-05-01

    The milk sphingomyelin (MSM) is involved in the formation of ordered lipid domains in the biological milk fat globule membrane (MFGM), where it accounts for about 30%wt of the polar lipids. Moreover, MSM exhibits a large variety in saturated acyl chain lengths (from C16:0 to C24:0-SM) compared to other natural sphingomyelins, which may impact the packing of MSM molecular species in the gel phase domains and the topography of the MFGM. To investigate this, supported lipid bilayers of synthetic sphingomyelins or of MSM-containing mixtures, including a MFGM polar lipid extract, were imaged at temperatures below the Tm of MSM (i.e. gel phase) in hydrated conditions using atomic force microscopy. In all compositions containing MSM, the MSM-rich gel phase domains exhibited lower and upper height levels H, interpreted as two distinct gel phases with ∆H~0.5-1.1nm. Two (lower and upper) gel phases were also found for pure C24:0-SM bilayers or for bilayers of a C16:0-SM/C24:0-SM equimolar mixture, while C16:0-SM bilayers were uniformly flat and less thick than C24:0-SM bilayers. The upper gel phase of MSM-containing bilayers was interpreted as mixed interdigitated C24:0-SM molecules, while the lower gel phase was attributed both to fully interdigitated C24:0-SM molecules and non-interdigitated C16:0-SM molecules. These results show that the composition of natural sphingomyelins, inducing a mismatch between the d18:1 sphingosine and the acyl chains, is important in both the internal organization and the topography of biological membranes, especially that of the MFGM. This organization could be involved in specific biological functions, e.g. the insertion of proteins.

  7. Interaction of dipalmitoyl phosphatidylcholine (DPPC) liposomes and insulin

    Science.gov (United States)

    Mady, Mohsen M.; Elshemey, Wael M.

    2011-06-01

    Insulin, a peptide that has been used for decades in the treatment of diabetes, has well-defined properties and delivery requirements. Liposomes, which are lipid bilayer vesicles, have gained increasing attention as drug carriers which reduce the toxicity and increase the pharmacological activity of various drugs. The molecular interaction between (uncharged lipid) dipalmitoyl phosphatidylcholine (DPPC) liposomes and insulin has been characterized by using Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. The characteristic protein absorption band peaks, Amide I (at about 1660 cm-1) and Amide II band (at about 1546 cm-1) are potentially reduced in the liposome insulin complex. Wide-angle x-ray scattering measurements showed that the association of insulin with DPPC lipid of liposomes still maintains the characteristic DPPC diffraction peaks with almost no change in relative intensities or change in peak positions. The absence of any shift in protein peak positions after insulin being associated with DPPC liposomes indicates that insulin is successfully forming complex with DPPC liposomes with possibly no pronounced alterations in the structure of insulin molecule.

  8. Phosphate mineral formation on the supported dipalmitoylphosphatidylcholine (DPPC) layers.

    Science.gov (United States)

    Szcześ, Aleksandra

    2014-07-01

    Dipalmitoylphosphatidylcholine (DPPC) mono- and bilayers supported on mica surface were soaked for two weeks in a simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma. Two solutions were investigated: with and without Tris. The experiment was conducted at 20°C and at a physiological temperature equal to 37°C. Raman spectroscopy was used for the characterization of the precipitated phosphate minerals. These studies may provide information about the physiological mineralization of cell membranes that are mainly composed of phospholipids. Findings from these experiments suggest that the DPPC bilayers enhance the formation of less soluble phosphate forms especially at a temperature of 37°C. In the solution without Tris temperature increase gives more mineral deposits. It is probably the hydrogen interactions between phosphate groups of the phospholipid and hydroxyl groups from Tris that lower exposure of the phosphate group to interact with calcium ions.

  9. Membrane fluidity and the surface properties of the lipid bilayer: ESR experiment and computer simulation.

    Science.gov (United States)

    Man, Dariusz; Olchawa, Ryszard; Kubica, Krystian

    2010-09-01

    Penetration of the liposome membranes formed in the gel phase from DPPC (DPPC liposomes) and in the liquid-crystalline phase from egg yolk lecithin (EYL liposomes) by the TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) and 16 DOXYL (2-ethyl-2-(15-methoxy-oxopentadecyl)-4,4-dimethyl-3-oxazolidinyloxy) spin probes has been investigated. The penetration process was followed by 120 hours at 24(0)C, using the electron spin resonance (ESR) method. The investigation of the kinetics of the TEMPO probe building into the membranes of both types of liposomes revealed differences appearing 30 minutes after the start of the experiment. The number of TEMPO particles built into the EYL liposome membranes began to clearly rise, aiming asymptotically to a constant value after about 100 minutes, whereas the number of the TEMPO particles built into the DPPC liposome membranes was almost constant in time. The interpretation of the obtained experimental results was enriched with those of computer simulation, following the behavior of the polar heads (dipoles) of the lipid particles forming a lipid layer due to the change in the value of the model parameter, k, determining the mobility of the dipoles. The possibility of the formation of an irregular ordering of the polar part of lipid membranes was proved, which leads to the appearance of spaces filled with of water for k > 0.4. The appearance of these defects enables the penetration of the bilayer by the TEMPO particles. The limited mobility of lipid polar heads (k < 0.2) prevents the appearance of such areas facilitating the penetration of the lipid membrane by alien particles in the gel phase.

  10. Alternative methods of determining phase transition temperatures of phospholipids that constitute liposomes on the example of DPPC and DMPC

    Energy Technology Data Exchange (ETDEWEB)

    Pentak, Danuta, E-mail: danuta.pentak@us.edu.pl

    2014-05-01

    Highlights: • New phase transition for DMPC was found. • FT-IR method is an important addition to the DSC studies. • The proposed method for determining the T{sub C} give very consistent results. - Abstract: In this work, alternatives to differential scanning calorimetry (DSC) as a method of determining the main phospholipid phase transition temperature are presented. The bilayer phase transitions from the ripple gel phase (P{sub β{sup ′}}) to the liquid-crystal phase (L{sub α}) of 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) were studied by differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) methods. In this work, two correlations between the DSC and FT-IR methods, and NMR and EPR methods are shown. The proposed methods allow for determining the T{sub C} temperature with a high degree of accuracy. Furthermore, a comparison of results obtained using the DSC and FT-IR methods allowed for an observation of a new DMPC phase transition. The liposomes analyzed in this work were obtained by the modified reverse-phase evaporation method (mREV)

  11. Comparison of DPPC and DPPG environments in pulmonary surfactant models.

    Science.gov (United States)

    Morrow, Michael R; Temple, Sara; Stewart, June; Keough, Kevin M W

    2007-07-01

    Deuterium nuclear magnetic resonance was used to monitor lipid acyl-chain orientational order in suspensions of dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylglycerol (DPPG) containing Ca(2+) and the lung surfactant proteins SP-A and SP-B separately and together. To distinguish between protein-lipid interactions involving the PC and PG lipid headgroups and to examine whether such interactions might influence spatial distribution of lipids within the bilayer, acyl chains on either the DPPC or the DPPG component of the mixture were deuterated. The lipid components of the resulting mixtures were thus either DPPC-d(62)/DPPG (7:3) or DPPC/DPPG-d(62) (7:3), respectively. SP-A had little effect on DPPC-d(62) chain order but did narrow the temperature range over which DPPG-d(62) ordered at the liquid-crystal-to-gel transition. No segregation of lipid components was seen for temperatures above or below the transition. Near the transition, though, there was evidence that SP-A promoted preferential depletion of DPPG from liquid crystalline domains in the temperature range over which gel and liquid crystal domains coexist. SP-B lowered average chain order of both lipids both above and below the main transition. The perturbations of chain order by SP-A and SP-B together were smaller than by SP-B alone. This reduction in perturbation of the lipids by the additional presence of SP-A likely indicated a strong interaction between SP-A and SP-B. The competitive lipid-lipid, lipid-protein, and protein-protein interactions suggested by these observations presumably facilitate the reorganization of surfactant material inherent in the transformation from lamellar bodies to a functional surfactant layer.

  12. Electron density analysis of the effects of sugars on the structure of lipid bilayers at low hydration - a preliminary study

    Energy Technology Data Exchange (ETDEWEB)

    Lenné, T.; Kent, B.; Koster, K.L.; Garvey, C.J.; Bryant, G. (ANSTO); (USD); (ANU); (RMIT)

    2012-02-06

    Small angle X-ray scattering is used to study the effects of sugars on membranes during dehydration. Previous work has shown that the bilayer and chain-chain repeat spacings of DPPC bilayers are relatively unaffected by the presence of sugars. In this work we present a preliminary analysis of the electron density profiles of DPPC in the presence of sugars at low hydration. The difficulties of determining the correct phasing are discussed. Sugars and other small solutes have been shown to have an important role in improving the tolerance of a range of species to desiccation and freezing. In particular it has been shown that sugars can stabilize membranes in the fluid membrane phase during dehydration, and in the fully dehydrated state. Equivalently, at a particular hydration, the presence of sugars lowers the transition temperature between the fluid and gel phases. There are two competing models for explaining the effects of sugars on membrane phase transition temperatures. One, designated the water replacement hypothesis (WRH) states that sugars hydrogen bond to phospholipid headgroups, thus hindering the fluid-gel phase transition. One version of this model suggests that certain sugars (such as trehalose) achieve the measured effects by inserting between the phospholipid head groups. An alternative model explains the observed effects of sugars in terms of the sugars effect on the hydration repulsion that develops between opposing membranes during dehydration. The hydration repulsion leads to a lateral compressive stress in the bilayer which squeezes adjacent lipids more closely together, resulting in a transition to the gel phase. When sugars are present, their osmotic and volumetric effects reduce the hydration repulsion, reduce the compressive stress in the membranes, and therefore tend to maintain the average lateral separation between lipids. This model is called the hydration forces explanation (HFE). We recently showed that neither mono- nor di

  13. Microstructural Phase Changes of DPPC-Ergosterol Supported Membranes Stressed by Ethanol

    Science.gov (United States)

    Vanegas, Juan; Block, David; Faller, Roland; Longo, Marjorie

    2010-03-01

    Microstructure of DPPC-Ergosterol supported lipid bilayers (SLBs) stressed by ethanol is examined at the nanoscopic level using atomic force microscopy (AFM). Alcohols such as ethanol are known to cause changes in the phase behavior of phospholipids as well as inducing the formation of an interdigitated phase of reduced thickness, where the hydrophobic tails of the top and bottom lipids intercalate causing an increase in the area per lipid as well as the solvent exposed surface of the headgroups. SLBs composed of 75-100 mole % 1,2-Dipalmitoyl-sn-Glycero-3-Phosphocholine (DPPC) and 0-25 mole % ergosterol were deposited on mica through the vesicle deposition method. In order to observe the ethanol-induced phase changes that can be observed in free bilayers, the vesicles must be prepared in buffer solution containing ethanol. The presence of salt is required to reduce the effect of the strong interaction between the bilayers and the support, which in the absence of ethanol and salt induces the formation of a tilted phase similar to the interdigitated phase in DPPC bilayers deposited above the melting temperature. As previously observer by other groups, ethanol-induced changes in SLBs often require heating above the transition temperature after addition of ethanol, or sample preparation in the presence of the alcohol. The later method was used as it produces more consistent results and the observations agree well with the previously reported phase diagram of DPPC-Ergosterol with ethanol.

  14. DPPC-cholesterol phase diagram using coarse-grained Molecular Dynamics simulations.

    Science.gov (United States)

    Wang, Yin; Gkeka, Paraskevi; Fuchs, Julian E; Liedl, Klaus R; Cournia, Zoe

    2016-11-01

    Cholesterol-phospholipid bilayers continue to be the current state of the art in membrane models and serve as representative systems for studying the effect of cholesterol on the cell membrane. As the mixing of different lipid species requires long spatio-temporal scales, coarse-grained models have gained increasing popularity in modeling such membrane systems. In this paper, a systematic study of the MARTINI coarse-grained model for the DPPC-cholesterol binary system has been performed. We construct the phase diagram of DPPC lipid bilayers in the presence of different cholesterol concentrations and at different temperatures using coarse-grained Molecular Dynamics (MD) simulations with the MARTINI force field. The phase diagram based on the condensation effect is directly comparable to available experimental data and demonstrates qualitative agreement over all cholesterol concentrations. Self-assembled bilayers quantitatively reproduce experimental observables, such as lateral diffusion of lipids, electron density, area per lipid and lipid order parameters. The phase diagram of the DPPC-cholesterol binary system also reveals the profound effect of cholesterol on the physical properties of phospholipid bilayers such lipid order, diffusion, and fluidity. Cholesterol induces the liquid-ordered phase, which increases the fluidity of the phospholipid hydrocarbon chains above the gel to liquid-crystalline phase transition temperature and decreases it below the phase transition. The present study suggests that the MARTINI force field can be successfully used to obtain molecular level insights into cholesterol-DPPC model membranes. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Interactions of Borneol with DPPC Phospholipid Membranes: A Molecular Dynamics Simulation Study

    Directory of Open Access Journals (Sweden)

    Qianqian Yin

    2014-11-01

    Full Text Available Borneol, known as a “guide” drug in traditional Chinese medicine, is widely used as a natural penetration enhancer in modern clinical applications. Despite a large number of experimental studies on borneol’s penetration enhancing effect, the molecular basis of its action on bio-membranes is still unclear. We carried out a series of coarse-grained molecular dynamics simulations with the borneol concentration ranging from 3.31% to 54.59% (v/v, lipid-free basis to study the interactions of borneol with aDPPC(1,2-dipalmitoylsn-glycero-3-phosphatidylcholine bilayer membrane, and the temperature effects were also considered. At concentrations below 21.89%, borneol’s presence only caused DPPC bilayer thinning and an increase in fluidity; A rise in temperature could promote the diffusing progress of borneol. When the concentration was 21.89% or above, inverted micelle-like structures were formed within the bilayer interior, which led to increased bilayer thickness, and an optimum temperature was found for the interaction of borneol with the DPPC bilayer membrane. These findings revealed that the choice of optimal concentration and temperature is critical for a given application in which borneol is used as a penetration enhancer. Our results not only clarify some molecular basis for borneol’s penetration enhancing effects, but also provide some guidance for the development and applications of new preparations containing borneol.

  16. Moving-window 2D correlation spectroscopy in studies of fluphenazine-DPPC dehydrated film as a function of temperature

    Science.gov (United States)

    Szwed, Joanna; Cieślik-Boczula, Katarzyna; Czarnik-Matusewicz, Bogusława; Jaszczyszyn, Agata; Gąsiorowski, Kazimierz; Świątek, Piotr; Malinka, Wiesław

    2010-06-01

    The effect of incorporating fluphenazine (FPh) into the dipalmitoylphosphatidylcholine (DPPC) multibilayers was studied by means of two-dimensional correlation spectroscopy (2DCOS) applied to attenuated total reflection (ATR) infrared spectra. DPPC is used as a model membrane that mimics the organization of lipids in biological membranes and their interaction with FPh. ATR-IR spectra for both DPPC dry film alone and the film doped with FPh were recorded as a function of temperature to provide information about the interaction between FPh molecules and DPPC lipid. The chain-melting phase-transition temperature changes are strictly correlated with the conformational order of the lipid hydrocarbon chains. To gain deeper insight into the accompanying spectral changes, we employed moving-window 2D correlation spectroscopy. Subdividing all the measurements from 10 to 90 °C into 20° subsets enables a detailed identification of spectral features induced by embedding FPh into DPPC multilayers. Moving-window analysis of the power spectra for the ν asym,symCH 2, δ sCH 2, and δ rCH 2 vibrations provides evidence that FPh is embedded in the region between the bilayers, penetrating their hydrophilic part, which destabilizes the interchain interaction. Above 60 °C the FPh-DPPC system reaches the liquid crystalline phase with the well-established location of FPh. A further temperature increase to 90 °C has little effect on the intrachain conformational order and the packing character of the FPh-DPPC system in the liquid crystalline phase. In addition, FPh hinders the formation of large domains. Comparison of the moving-window analysis done by using slice spectra for DPPC and FPh-doped DPPC dry film for ν asym,symCH 2, νC dbnd O, and νPO2- shows that the interaction between the DPPC and FPh molecules is accompanied by very distinct spectral changes located in a both lower and narrower temperature range than those observed in pure DPPC film.

  17. Effect of substitution of hydrogen oxide by deuterium oxide on thermotropic transition between the interdigitated gel phase and the ripple phase of dihexadecylphosphatidylcholine

    Energy Technology Data Exchange (ETDEWEB)

    Ohki, K. (Nagoya Univ. (Japan))

    1991-01-15

    Thermotropic transitions of dihexadecylphosphatidylcholine (DHPC) dispersions in hydrogen oxide (1H2O) and deuterium oxide (2H2O) were investigated by differential scanning calorimetry (DSC). In DHPC dispersions, transition temperature between interdigitated gel phase (L beta I) and ripple phase (P beta') is lower in 2H2O than in 1H2O, and transition between the ripple phase (P beta') and fluid phase (L alpha) in 2H2O occurs at a temperature slightly higher than in 1H2O. In dipalmitoylphosphatidylcholine (DPPC) dispersions, on the other hand, transition temperature between lamellar gel phase (L beta') and ripple phase is higher in 2H2O than in 1H2O. These results suggest that the interdigitated gel phase is more stable in 1H2O than in 2H2O. To account for the shift of transition temperature by the water substitution, difference of interfacial energies between these aqueous environments is discussed.

  18. Differential ability of cholesterol-enriched and gel phase domains to resist benzyl alcohol-induced fluidization in multilamellar lipid vesicles.

    Science.gov (United States)

    Maula, Terhi; Westerlund, Bodil; Slotte, J Peter

    2009-11-01

    Benzyl alcohol (BA) has a well-known fluidizing effect on both artificial and cellular membranes. BA is also likely to modulate the activities of certain membrane proteins by decreasing the membrane order. This phenomenon is presumably related to the ability of BA to interrupt interactions between membrane proteins and the surrounding lipids by fluidizing the lipid bilayer. The components of biological membranes are laterally diversified into transient assemblies of varying content and order, and many proteins are suggested to be activated or inactivated by their localization in or out of membrane domains displaying different physical phases. We studied the ability of BA to fluidize artificial bilayer membranes representing liquid-disordered, cholesterol-enriched and gel phases. Multilamellar vesicles were studied by steady-state fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene and trans-parinaric acid, which display different phase partitioning. Domains of different degree of order and thermal stability showed varying abilities to resist fluidization by BA. In bilayers composed of mixtures of an unsaturated phosphatidylcholine, a saturated high melting temperature lipid (sphingomyelin or phosphatidylcholine) and cholesterol, BA fluidized and lowered the melting temperature of the ordered and gel phase domains. In general, cholesterol-enriched domains were more resistant to BA than pure gel phase domains. In contrast, bilayers containing high melting temperature gel phase domains containing a ceramide or a galactosylceramide proved to be the most effective in resisting fluidization. The results of our study suggest that the ability of BA to affect the fluidity and lateral organization of the membranes was dependent on the characteristic features of the membrane compositions studied and related to the intermolecular cohesion in the domains.

  19. In situ atomic force microscope imaging of supported lipid bilayers

    DEFF Research Database (Denmark)

    Kaasgaard, Thomas; Leidy, Chad; Ipsen, John Hjorth

    2001-01-01

    In situ AFM images of phospholipase A/sub 2/ (PLA/sub 2/) hydrolysis of mica-supported one- and two-component lipid bilayers are presented. For one-component DPPC bilayers an enhanced enzymatic activity is observed towards preexisting defects in the bilayer. Phase separation is observed in two......-component DMPC-DSPC bilayers and a remarkable enhanced hydrolytic activity of the PLA/sub 2/-enzyme for the DMPC-rich phase is seen. Furthermore, in a supported double bilayer system a characteristic ripple structure, most likely related to the formation of the P/sub beta /-ripple phase is observed....

  20. Improvement in physicochemical parameters of DPPC liposomes and increase in skin permeation of aciclovir and minoxidil by the addition of cationic polymers.

    Science.gov (United States)

    Hasanovic, Amra; Hollick, Caroline; Fischinger, Kerstin; Valenta, Claudia

    2010-06-01

    1,2-Dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) liposomes were prepared by high-pressure homogeniser and coated with two cationic polymers, chitosan (CS) and for the first time Eudragit EPO (EU), respectively. Compared to the control liposomes, the polymeric liposomes showed greater physicochemical stability in terms of mean particle size and zeta potential at room temperature. In the present study, aciclovir and minoxidil have been used as hydrophilic and hydrophobic candidates. In the presence of the drugs, the polymeric liposomes still showed constant particle size and zeta potential. Influences of polymers and model drugs on thermotropic phase transition of DPPC liposomes were studied by micro-differential scanning calorimetry (microDSC). The influences on configuration of DPPC liposomes were investigated by Fourier transform infrared spectroscopy (FTIR). According to DSC results, cationic polymers had a stabilising effect, whereas aciclovir and minoxidil changed the physical properties of the DPPC bilayers by influencing the main phase transition temperature and erasing the pre-transition. The investigation of CO stretching bands of DPPC at 1736 cm(-1) in FTIR spectra showed that aciclovir has strong hydrogen bonding with CO groups of DPPC, whereas carbonyl groups were free in minoxidil presence. Moreover, the coating of liposomes with CS or EU led to higher skin diffusion for both drugs. This could be explained as an effect of positively charged liposomes to interact stronger with skin negatively charged surface and their possible interactions with structures below the stratum corneum. Copyright 2010 Elsevier B.V. All rights reserved.

  1. Temperature-controlled structure and kinetics of ripple phases in one- and two-component supported lipid bilayers

    DEFF Research Database (Denmark)

    Kaasgaard, Thomas; Leidy, Chad; Crowe, J.H.

    2003-01-01

    ripples was seen. From height profiles of the AFM images, estimates of the amplitudes of the different ripple phases are reported. To elucidate the processes of ripple formation and disappearance, a ripple-phase DPPC lipid bilayer was taken through the pretransition in the cooling and the heating......Temperature-controlled atomic force microscopy (AFM) has been used to visualize and study the structure and kinetics of ripple phases in one-component dipalmitoylphosphaticlylcholine (DPPC) and two-component dimyristoylphosphatidylcholine-distearoylphosphatidylcholine (DMPC-DSPC) lipid bilayers....... The lipid bilayers are mica-supported double bilayers in which ripple-phase formation occurs in the top bilayer. In one-component DPPC lipid bilayers, the stable and metastable ripple phases were observed. In addition, a third ripple structure with approximately twice the wavelength of the metastable...

  2. Study of Raft Domains in Model Membrane of DPPC/PE/Cholesterol

    Science.gov (United States)

    Lor, Chai; Hirst, Linda

    2010-10-01

    Raft domains in bilayer membrane are thought to play an important role in many cell functions such as cell signaling or trans-membrane protein activation. Here we use a model membrane consisting of DPPC/PE/cholesterol to examine the structure of membrane rafts and phase interactions. In particular we are interested in lipids containing the highly polyunsaturated fatty acid DHA. We use both atomic force microscopy (AFM) and fluorescence microscopy to obtain information on the structural properties of raft regions and track cholesterol. As expected, we find phase separation of raft regions between saturated and unsaturated lipids. Moreover, we find that the roughness of the domains change with varying cholesterol concentration possibly due to overpacking. This model study provides further understanding of the role of cholesterol in bilayer membrane leading towards a better knowledge of cell membranes.

  3. Structural Effects of Small Molecules on Phospholipid Bilayers Investigated by Molecular Simulations

    CERN Document Server

    Lee, B W; Sum, A K; Vattulainen, I; Patra, M; Karttunen, M; Lee, Bryan W; Faller, Roland; Sum, Amadeu K; Vattulainen, Ilpo; Patra, Michael; Karttunen, Mikko

    2004-01-01

    We summarize and compare recent Molecular Dynamics simulations on the interactions of dipalmitoylphosphatidylcholine (DPPC) bilayers in the liquid crystalline phase with a number of small molecules including trehalose, a disaccharide of glucose, alcohols, and dimethylsulfoxide (DMSO). The sugar molecules tend to stabilize the structure of the bilayer as they bridge adjacent lipid headgroups. They do not strongly change the structure of the bilayer. Alcohols and DMSO destabilize the bilayer as they increase its area per molecule in the bilayer plane and decrease the order parameter. Alcohols have a stronger detrimental effect than DMSO. The observables which we compare are the area per molecule in the plane of the bilayer, the membrane thickness, and the NMR order parameter of DPPC hydrocarbon tails. The area per molecule and the order parameter are very well correlated whereas the bilayer thickness is not necessarily correlated with them.

  4. Gel phase formation in dilute triblock copolyelectrolyte complexes

    Science.gov (United States)

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-02-01

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

  5. Towards bio-silicon interfaces: formation of an ultra-thin self-hydrated artificial membrane composed of dipalmitoylphosphatidylcholine (DPPC) and chitosan deposited in high vacuum from the gas-phase.

    Science.gov (United States)

    Retamal, María J; Cisternas, Marcelo A; Gutierrez-Maldonado, Sebastian E; Perez-Acle, Tomas; Seifert, Birger; Busch, Mark; Huber, Patrick; Volkmann, Ulrich G

    2014-09-14

    The recent combination of nanoscale developments with biological molecules for biotechnological research has opened a wide field related to the area of biosensors. In the last years, device manufacturing for medical applications adapted the so-called bottom-up approach, from nanostructures to larger devices. Preparation and characterization of artificial biological membranes is a necessary step for the formation of nano-devices or sensors. In this paper, we describe the formation and characterization of a phospholipid bilayer (dipalmitoylphosphatidylcholine, DPPC) on a mattress of a polysaccharide (Chitosan) that keeps the membrane hydrated. The deposition of Chitosan (~25 Å) and DPPC (~60 Å) was performed from the gas phase in high vacuum onto a substrate of Si(100) covered with its native oxide layer. The layer thickness was controlled in situ using Very High Resolution Ellipsometry (VHRE). Raman spectroscopy studies show that neither Chitosan nor DPPC molecules decompose during evaporation. With VHRE and Atomic Force Microscopy we have been able to detect phase transitions in the membrane. The presence of the Chitosan interlayer as a water reservoir is essential for both DPPC bilayer formation and stability, favoring the appearance of phase transitions. Our experiments show that the proposed sample preparation from the gas phase is reproducible and provides a natural environment for the DPPC bilayer. In future work, different Chitosan thicknesses should be studied to achieve a complete and homogeneous interlayer.

  6. Towards bio-silicon interfaces: Formation of an ultra-thin self-hydrated artificial membrane composed of dipalmitoylphosphatidylcholine (DPPC) and chitosan deposited in high vacuum from the gas-phase

    Energy Technology Data Exchange (ETDEWEB)

    Retamal, María J., E-mail: moretama@uc.cl; Cisternas, Marcelo A.; Seifert, Birger; Volkmann, Ulrich G. [Instituto de Física, Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, 7820436 Santiago (Chile); Centro de Investigación en Nanotecnología y Materiales Avanzados (CIEN-UC), Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, 7820436 Santiago (Chile); Gutierrez-Maldonado, Sebastian E.; Perez-Acle, Tomas [Computational Biology Lab (DLab), Fundación Ciencia y Vida, Av. Zañartu 1482, Santiago (Chile); Centro Interdisciplinario de Neurociencias de Valparaiso (CINV), Universidad de Valparaiso, Pasaje Harrington 287, Valparaiso (Chile); Busch, Mark; Huber, Patrick [Institute of Materials Physics and Technology, Hamburg University of Technology (TUHH), D-21073 Hamburg-Harburg (Germany)

    2014-09-14

    The recent combination of nanoscale developments with biological molecules for biotechnological research has opened a wide field related to the area of biosensors. In the last years, device manufacturing for medical applications adapted the so-called bottom-up approach, from nanostructures to larger devices. Preparation and characterization of artificial biological membranes is a necessary step for the formation of nano-devices or sensors. In this paper, we describe the formation and characterization of a phospholipid bilayer (dipalmitoylphosphatidylcholine, DPPC) on a mattress of a polysaccharide (Chitosan) that keeps the membrane hydrated. The deposition of Chitosan (∼25 Å) and DPPC (∼60 Å) was performed from the gas phase in high vacuum onto a substrate of Si(100) covered with its native oxide layer. The layer thickness was controlled in situ using Very High Resolution Ellipsometry (VHRE). Raman spectroscopy studies show that neither Chitosan nor DPPC molecules decompose during evaporation. With VHRE and Atomic Force Microscopy we have been able to detect phase transitions in the membrane. The presence of the Chitosan interlayer as a water reservoir is essential for both DPPC bilayer formation and stability, favoring the appearance of phase transitions. Our experiments show that the proposed sample preparation from the gas phase is reproducible and provides a natural environment for the DPPC bilayer. In future work, different Chitosan thicknesses should be studied to achieve a complete and homogeneous interlayer.

  7. Towards bio-silicon interfaces: Formation of an ultra-thin self-hydrated artificial membrane composed of dipalmitoylphosphatidylcholine (DPPC) and chitosan deposited in high vacuum from the gas-phase

    Science.gov (United States)

    Retamal, María J.; Cisternas, Marcelo A.; Gutierrez-Maldonado, Sebastian E.; Perez-Acle, Tomas; Seifert, Birger; Busch, Mark; Huber, Patrick; Volkmann, Ulrich G.

    2014-09-01

    The recent combination of nanoscale developments with biological molecules for biotechnological research has opened a wide field related to the area of biosensors. In the last years, device manufacturing for medical applications adapted the so-called bottom-up approach, from nanostructures to larger devices. Preparation and characterization of artificial biological membranes is a necessary step for the formation of nano-devices or sensors. In this paper, we describe the formation and characterization of a phospholipid bilayer (dipalmitoylphosphatidylcholine, DPPC) on a mattress of a polysaccharide (Chitosan) that keeps the membrane hydrated. The deposition of Chitosan (˜25 Å) and DPPC (˜60 Å) was performed from the gas phase in high vacuum onto a substrate of Si(100) covered with its native oxide layer. The layer thickness was controlled in situ using Very High Resolution Ellipsometry (VHRE). Raman spectroscopy studies show that neither Chitosan nor DPPC molecules decompose during evaporation. With VHRE and Atomic Force Microscopy we have been able to detect phase transitions in the membrane. The presence of the Chitosan interlayer as a water reservoir is essential for both DPPC bilayer formation and stability, favoring the appearance of phase transitions. Our experiments show that the proposed sample preparation from the gas phase is reproducible and provides a natural environment for the DPPC bilayer. In future work, different Chitosan thicknesses should be studied to achieve a complete and homogeneous interlayer.

  8. Probing lipid-cholesterol interactions in DOPC/eSM/Chol and DOPC/DPPC/Chol model lipid rafts with DSC and (13)C solid-state NMR.

    Science.gov (United States)

    Fritzsching, Keith J; Kim, Jihyun; Holland, Gregory P

    2013-08-01

    The interaction between cholesterol (Chol) and phospholipids in bilayers was investigated for the ternary model lipid rafts, DOPC/eSM/Chol and DOPC/DPPC/Chol, with differential scanning calorimetry (DSC) and (13)C cross polarization magic angle spinning (CP-MAS) solid-state NMR. The enthalpy and transition temperature (Tm) of the Lα liquid crystalline phase transition from DSC was used to probe the thermodynamics of the different lipids in the two systems as a function of Chol content. The main chain (13)C (CH2)n resonance is resolved in the (13)C CP-MAS NMR spectra for the unsaturated (DOPC) and saturated (eSM or DPPC) chain lipid in the ternary lipid raft mixtures. The (13)C chemical shift of this resonance can be used to detect differences in chain ordering and overall interactions with Chol for the different lipid constituents in the ternary systems. The combination of DSC and (13)C CP-MAS NMR results indicate that there is a preferential interaction between SM and Chol below Tm for the DOPC/eSM/Chol system when the Chol content is ≤20mol%. In contrast, no preferential interaction between Chol and DPPC is observed in the DOPC/DPPC/Chol system above or below Tm. Finally, (13)C CP-MAS NMR resolves two Chol environments in the DOPC/eSM/Chol system below Tm at Chol contents >20mol% while, a single Chol environment is observed for DOPC/DPPC/Chol at all compositions.

  9. Gel phase formation in dilute triblock copolyelectrolyte complexes

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Samanvaya; Andreev, Marat; Levi, Adam E.; Goldfeld, David J.; Mao, Jun; Heller, William T.; Prabhu, Vivek M.; de Pablo, Juan J.; Tirrell, Matthew V.

    2017-02-23

    Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

  10. A comparative differential scanning calorimetry study of the effects of cholesterol and various oxysterols on the thermotropic phase behavior of dipalmitoylphosphatidylcholine bilayer membranes.

    Science.gov (United States)

    Benesch, Matthew G K; McElhaney, Ronald N

    2016-02-01

    We have carried out a comparative differential scanning calorimetric (DSC) study of the effects of cholesterol (C) and the eight most physiologically relevant oxysterols on the thermotropic phase behavior of dipalmitoylphosphatidylcholine (DPPC) bilayer membranes. The structures of these oxysterols differ from that of C by the presence of additional hydroxyl, keto or epoxy groups on the steroid ring system or by the presence of a hydroxyl group in the alkyl side chain. In general, the progressive incorporation of these oxysterols reduces the temperature, cooperativity and enthalpy of the pretransition of DPPC to a greater extent than C, indicating that their presence thermally destabilizes and disorders the gel states of DPPC bilayers to a greater extent than C. Similarly, the incorporation of these oxysterols either increases the temperature of the broad component of the main phase transition to a smaller extent than C or actually decreases it. Again, this indicates that the presence of these compounds is less effective at thermally stabilizing and ordering the sterol-rich domains of DPPC bilayers than is C itself. Moreover, the incorporation of these oxysterols decrease the cooperativity and enthalpy of the main phase transition of DPPC to a smaller extent than C, indicating that they are somewhat less miscible in fluid DPPC bilayers than is C. Particularly notable in this regard is 25-hydroxycholesterol, which exhibits a markedly reduced miscibility in both gel and fluid DPPC bilayers compared to C itself. In general, the effectiveness of these oxysterols in stabilizing and ordering DPPC bilayers decreases as their rate of interbilayer exchange and the polarity of the oxysterol increases. We close by providing a tentative molecular explanation for the results of our DSC studies and of those of previous biophysical studies of the effects of various oxysterol on lipid bilayer model membranes. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  11. Chain elongation of diacylphosphatidylcholine induces fully bilayer interdigitation under atmospheric pressure.

    Science.gov (United States)

    Goto, Masaki; Wilk, Agnieszka; Kazama, Akira; Chodankar, Shirish; Kohlbrecher, Joachim; Matsuki, Hitoshi

    2011-05-01

    The phase transitions of dibehenoylphosphatidylcholine (C22PC) bilayer membrane were observed by differential scanning calorimetry under atmospheric pressure and light-transmittance measurements under high pressure. The constructed temperature-pressure phase diagram suggests that the gel phase at low temperatures is the interdigitated gel phase. To confirm the phase state, we performed small-angle neutron scattering and fluorescence measurements using a polarity-sensitive probe Prodan for the C22PC bilayer membrane under atmospheric pressure. The peaks obtained in both measurements clearly showed the characteristic patterns of the fully interdigitated gel phase. Taking into account of previous studies on the gel phase for long-chain PC bilayers under atmospheric pressure and our studies on the pressure-induced bilayer interdigitaion of diacyl-PCs, it turned out that the interdigitation of diacyl-PC bilayer membranes occurs when the carbon number of acyl chain reaches at least 22. The present study revealed that the interdigitation of PC bilayer membranes occurs not only by weakening the attractive force of polar head groups but also by strengthening the cohesive force of acyl chains. When dominating the force of acyl chains, the interdigitation can be induced even in a diacyl-PC bilayer membrane by only hydration under atmospheric pressure.

  12. Methodological problems in pressure profile calculations for lipid bilayers

    DEFF Research Database (Denmark)

    Sonne, Jacob; Hansen, Flemming Yssing; Peters, Günther H.J.

    2005-01-01

    From molecular dynamics simulations of a dipalmitoyl-phosphatidyl-choline (DPPC) lipid bilayer in the liquid crystalline phase, pressure profiles through the bilayer are calculated by different methods. These profiles allow us to address two central and unresolved problems in pressure profile...... calculations: The first problem is that the pressure profile is not uniquely defined since the expression for the local pressure involves an arbitrary choice of an integration contour. We have investigated two different choices leading to the Irving-Kirkwood (IK) and Harasima (H) expressions for the local...... pressure tensor. For these choices we find that the pressure profile is almost independent of the contour used, which indicates that the local pressure is well defined for a DPPC bilayer in the liquid crystalline phase. This may not be the case for other systems and we therefore suggest that both the IK...

  13. Structural transition in aqueous lipid/bile salt [DPPC/NaDC] supramolecular aggregates: SANS and DLS study

    Energy Technology Data Exchange (ETDEWEB)

    Kiselev, M.A. [Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna (Russian Federation); Janich, M.; Hildebrand, A. [Martin-Luther-University, Halle (Saale) (Germany); Strunz, P. [Berlin Neutron Scattering Center, HZB, Berlin (Germany); Neubert, R.H.H. [Martin-Luther-University, Halle (Saale) (Germany); Lombardo, D., E-mail: lombardo@me.cnr.it [CNR–IPCF, Istituto per i Processi Chimico Fisici – (Sez. Messina), I-98158, Messina (Italy)

    2013-10-16

    Highlights: • Self-assembly in model DPPC lipids and NaDC bile salt by SANS and DLS experiments. • Bile salt creates structural interference against cohesive tendency of DPPC bilayers. • NaDC steric interactions cause transition toward different supramolecular structures. - Abstract: Small angle neutron scattering (SANS) and dynamic light scattering (DLS) were used to study different aggregation states in sodium deoxycholate (NaDC)-phosphatidylcholine systems at T = 60 °C. Size and shape of the aggregates investigated as a function of the NaDC bile salt concentration (at the constant DPPC concentration of 6 mM) indicate a strong dependence of the size and morphology of the generated aggregates on the relative amount of NaDC bile salt. More specifically large occupied area of the bile salt induces a steric interaction which promotes the transition toward a variety of supramolecular structures ranging from ellipsoidal vesicles, ribbon-like structures, up to final spherical mixed micelles at the large amount of bile salt of 10 mM NaDC. The findings of the obtained results give important insight for understanding the formation of different topologies in aqueous lipid–bile salt mixtures as well as stimulate new routes for liposome reconstitution–solubilisation processes suitable for technological applications.

  14. Multiscale molecular modeling of tertiary supported lipid bilayers

    Science.gov (United States)

    Ranz, Holden T.; Faller, Roland

    2015-08-01

    Ternary lipid bilayer systems assembled from mixtures of dipalmitoylphosphatidylcholine (DPPC), dioleoylphosphatidylcholine (DOPC), and cholesterol have been studied using coarse-grained molecular dynamics at biologically relevant temperatures (280 K to 310 K), which are between the chain melting temperatures of the pure lipid component. Free lipid bilayers were simulated using the MARTINI model (Stage I) and a variant with water-water interactions reduced to 76% (Stage II). The latter was subsequently used for preparing supported lipid bilayer simulations (Stage III). Clustering of like lipids was observed, but the simulation timescale did not yield larger phaseseparated domains.

  15. Trehalose-induced destabilization of interdigitated gel phase in dihexadecylphosphatidylcholine.

    Science.gov (United States)

    Takahashi, H; Ohmae, H; Hatta, I

    1997-01-01

    Trehalose is believed to have the ability to protect some organisms against low temperatures. To clarify the cryoprotective mechanism of trehalose, the structure and the phase behavior of fully hydrated dihexadecylphosphatidylcholine (DHPC) membranes in the presence of various concentrations of trehalose were studied by means of differential scanning calorimetry (DSC), static x-ray diffraction, and simultaneous x-ray diffraction and DSC measurements. The temperature of the interdigitated gel (Lbeta(i))-to-ripple (Pbeta') phase transition of DHPC decreases with a rise in trehalose concentration up to approximately 1.0 M. Above a trehalose concentration of approximately 1.0 M, no Lbeta(i) phase is observed. In this connection, the electron density profile calculated from the lamellar diffraction data in the presence of 1.6 M trehalose indicates that DHPC forms noninterdigitated bilayers below the P beta' phase. It was concluded that trehalose destabilizes the Lbeta(i) phase of DHPC bilayers. This suggests that trehalose reduces the area at the interface between the lipid and water. The relation between this effect of trehalose and a low temperature tolerance was discussed from the viewpoint of cold-induced denaturation of proteins. PMID:9414217

  16. Mixed DPPC/DPPG monolayers at very high film compression.

    Science.gov (United States)

    Saad, Sameh M I; Policova, Zdenka; Acosta, Edgar J; Hair, Michael L; Neumann, A Wilhelm

    2009-09-15

    A drop shape technique using a constrained sessile drop constellation (ADSA-CSD) has been introduced as a superior technique for studying spread films specially at high collapse pressures [Saad et al. Langmuir 2008, 24, 10843-10850]. It has been shown that ADSA-CSD has certain advantages including the need only for small quantities of liquid and insoluble surfactants, the ability to measure very low surface tension values, easier deposition procedure, and leak-proof design. Here, this technique was applied to investigate mixed DPPC/DPPG monolayers to characterize the role of such molecules in maintaining stable film properties and surface activity of lung surfactant preparations. Results of compression isotherms were obtained for different DPPC/DPPG mixture ratios: 90/10, 80/20, 70/30, 60/40, and 50/50 in addition to pure DPPC and pure DPPG at room temperature of 24 degrees C. The ultimate collapse pressure of DPPC/DPPG mixtures was found to be 70.5 mJ/m2 (similar to pure DPPC) for the cases of low DPPG content (up to 20%). Increasing the DPPG content in the mixture (up to 40%) caused a slight decrease in the ultimate collapse pressure. However, further increase of DPPG in the mixture (50% or more) caused a sharp decrease in the ultimate collapse pressure to a value of 59.9 mJ/m2 (similar to pure DPPG). The change in film elasticity was also tracked for the range of mixture ratios studied. The physical reasons for such changes and the interaction between DPPC and DPPG molecules are discussed. The results also show a change in the film hysteresis upon successive compression and expansion cycles for different mixture ratios.

  17. Phase coexistence in films composed of DLPC and DPPC: a comparison between different model membrane systems.

    Science.gov (United States)

    Mangiarotti, Agustín; Caruso, Benjamín; Wilke, Natalia

    2014-07-01

    For the biophysical study of membranes, a variety of model systems have been used to measure the different parameters and to extract general principles concerning processes that may occur in cellular membranes. However, there are very few reports in which the results obtained with the different models have been compared. In this investigation, we quantitatively compared the phase coexistence in Langmuir monolayers, freestanding bilayers and supported films composed of a lipid mixture of DLPC and DPPC. Two-phase segregation was observed in most of the systems for a wide range of lipid proportions using fluorescence microscopy. The lipid composition of the coexisting phases was determined and the distribution coefficient of the fluorescent probe in each phase was quantified, in order to explore their thermodynamic properties. The comparison between systems was carried out at 30mN/m, since it is accepted that at this or higher lateral pressures, the mean molecular area in bilayers is equivalent to that observed in monolayers. Our study showed that while Langmuir monolayers and giant unilamellar vesicles had a similar phase behavior, supported films showed a different composition of the phases with the distribution coefficient of the fluorescent probe being close to unity. Our results suggest that, in supported membranes, the presence of the rigid substrate may have led to a stiffening of the liquid-expanded phase due to a loss in the degrees of freedom of the lipids as a consequence of the proximity of the solid material.

  18. Asymmetric heat transfer from nanoparticles in lipid bilayers

    Science.gov (United States)

    Potdar, Dipti; Sammalkorpi, Maria

    2015-12-01

    Here, we use molecular dynamics simulations to characterize the heat transfer properties of lipid bilayer - gold nanoparticle systems in which the nanoparticle acts as a heat source. The focus is on dipalmitoylphosphatidylcholine (DPPC) lipid bilayers and thiolated alcohol and alkyl functionalized nanoparticles as prototype hydrophilic and hydrophobic nanoparticles. We find hydrophilic nanoparticles which are partly in contact with the surrounding water environment are more efficient in transferring heat to the system than hydrophobic ones which reside surrounded by the membrane. This is because of the hydrogen bonding capability of the hydroxy pentanethiol and the more efficient heat conductivity through water than the lipid bilayer. Additionally, we find the heat conductance is strongly asymmetric and has a discontinuity between the bilayer leaflets. In total, the findings provide understanding on heat transport from localized heat sources in lipid bilayers and could bear significance, e.g., in engineering and controlling photoactivated triggering of liposomal systems.

  19. Thermotropic and Barotropic Phase Behavior of Phosphatidylcholine Bilayers

    Directory of Open Access Journals (Sweden)

    Nobutake Tamai

    2013-01-01

    Full Text Available Bilayers formed by phospholipids are frequently used as model biological membranes in various life science studies. A characteristic feature of phospholipid bilayers is to undergo a structural change called a phase transition in response to environmental changes of their surroundings. In this review, we focus our attention on phase transitions of some major phospholipids contained in biological membranes, phosphatidylcholines (PCs, depending on temperature and pressure. Bilayers of dipalmitoylphosphatidylcholine (DPPC, which is the most representative lipid in model membrane studies, will first be explained. Then, the bilayer phase behavior of various kinds of PCs with different molecular structures is revealed from the temperature–pressure phase diagrams, and the difference in phase stability among these PC bilayers is discussed in connection with the molecular structure of the PC molecules. Furthermore, the solvent effect on the phase behavior is also described briefly.

  20. Texture of lipid bilayer domains

    DEFF Research Database (Denmark)

    Jensen, Uffe Bernchou; Brewer, Jonathan R.; Midtiby, Henrik Skov

    2009-01-01

    chains. By imaging the intensity variations as a function of the polarization angle, we map the lateral variations of the lipid tilt within domains. Results reveal that gel domains are composed of subdomains with different lipid tilt directions. We have applied a Fourier decomposition method......We investigate the texture of gel (g) domains in binary lipid membranes composed of the phospholipids DPPC and DOPC. Lateral organization of lipid bilayer membranes is a topic of fundamental and biological importance. Whereas questions related to size and composition of fluid membrane domain...... are well studied, the possibility of texture in gel domains has so far not been examined. When using polarized light for two-photon excitation of the fluorescent lipid probe Laurdan, the emission intensity is highly sensitive to the angle between the polarization and the tilt orientation of lipid acyl...

  1. Differential Effects of Cholesterol, Ergosterol and Lanosterol on a Dipalmitoyl Phosphatidylcholine (DPPC) membrane: A Molecular Dynamics Simulations Study

    Energy Technology Data Exchange (ETDEWEB)

    Cournia, Zoe [Yale University; Ullmann, G. Matthias [University of Bayreuth; Smith, Jeremy C [ORNL

    2007-02-01

    Lipid raft/domain formation may arise as a result of the effects of specific sterols on the physical properties of membranes. Here, using molecular dynamics simulation, we examine the effects of three closely-related sterols, ergosterol, cholesterol, and lanosterol, at a biologically relevant concentration (40 mol %) on the structural properties of a model dipalmitoyl phosphatidylcholine (DPPC) membrane at 309 and 323 K. All three sterols are found to order the DPPC acyl tails and condense the membrane relative to the DPPC liquid-phase membrane, but each one does this to a significantly different degree. The smooth {alpha}-face of ergosterol, together with the presence of tail unsaturation in this sterol, leads to closer interaction of ergosterol with the lipids and closer packing of the lipids with each other, so ergosterol has a higher condensing effect on the membrane, as reflected by the area per lipid. Moreover, ergosterol induces a higher proportion of trans lipid conformers, a thicker membrane, and higher lipid order parameters and is aligned more closely with the membrane normal. Ergosterol also positions itself closer to the bilayer/water interface. In contrast, the rough {alpha}-face of lanosterol leads to a less close interaction of the steroid ring system with the phospholipid acyl chains, and so lanosterol orders, straightens, and packs the lipid acyl chains less well and is less closely aligned with the membrane normal. Furthermore, lanosterol lies closer to the relatively disordered membrane center than do the other sterols. The behavior of cholesterol in all the above respects is intermediate between that of lanosterol and ergosterol. The findings here may explain why ergosterol is the most efficient of the three sterols at promoting the liquid-ordered phase and lipid domain formation and may also furnish part of the explanation as to why cholesterol is evolutionarily preferred over lanosterol in higher-vertebrate plasma membranes.

  2. Electric field-induced orientation of L- and DL-phosphatidylcholine bilayers.

    Science.gov (United States)

    Mishima, Kiyoshi; Tanaka, Shinobu; Ogihara, Toshihiko

    2002-09-20

    Membrane orientation induced by an alternating electric field has been examined for the L-enantiomer and racemic dipalmitoylphosphatidylcholine (DPPC) bilayers. The orientation effect was measured by bending curvature of hairpin-like deformation of the multilamellar cylindrical tubes with varying field-strength, frequency and tube size. It has been observed that both L- and DL-DPPC tubes are similar in the profiles of field-strength dependence and frequency dependence on the curvature deformation, but different in the deformed curvatures. DL-DPPC tubes deform largely as compared with L-DPPC tubes. The square of the deformed curvature of DL-DPPC tubes is larger than that of L-DPPC by about 37% on average. The result indicates that the racemic membrane is responsive to the electric field as compared with the L-enantiomer membrane. This suggests that a hybrid arrangement of head groups of the racemic lipid leads an effective response of the membrane due to the head group orientation.

  3. Patterning of Nanocrystalline Cellulose Gel Phase by Electrodissolution of a Metallic Electrode

    Science.gov (United States)

    Daignan, Jean-Michel; Chen, Ran; Mahmoud, Khaled A.; Ma, Yuan; Hill, Ian G.; Kreplak, Laurent

    2014-01-01

    At high concentration or in the presence of electrolytes and organic solvents, solutions of cellulose nanocrystals (CNCs) can form gels exhibiting optical properties similar to the ones of liquid crystal phases. In an attempt to pattern such a gel phase, we have studied the electrodissolution of a metallic electrode in a water suspension of carboxylated CNCs (cCNCs). Depending on the metal used, the electrodissolution process was observed at a different positive potential. In the case of copper the minimum potential at which we could observe optically the growth of the gel phase was 200 mV. The growth rate was current limited indicating that the process was controlled by the electrodissolution of the copper electrode. This hypothesis was confirmed by using circular and square copper patterns as positive electrodes. In both cases, the consumption of the electrode material was observed optically and correlated with the growth of the gel phase. PMID:24897116

  4. Molecular dynamics of dibenz[a,h]anthracene and its metabolite interacting with lung surfactant phospholipid bilayers.

    Science.gov (United States)

    Padilla-Chavarría, Helmut I; Guizado, Teobaldo R C; Pimentel, Andre S

    2015-08-28

    The interaction of dibenz[a,h]anthracene and its ultimate carcinogenic 3,4-diol-1,2-epoxide with lung surfactant phospholipid bilayers was successfully performed using molecular dynamics. The DPPC/DPPG/cholesterol bilayer (64 : 64 : 2) was used as the lung surfactant phospholipid bilayer model and compared with the DPPC bilayer as a reference. Dibenz[a,h]anthracene and its 3,4-diol-1,2-epoxide were inserted in water and lipid phases in order to investigate their interactions with the lung surfactant phospholipid bilayers. The radial distribution function between two P atoms in polar heads shows that the 3,4-diol-1,2-epoxide affects the order between the P atoms in the DPPC/DPPG/cholesterol model more than dibenz[a,h]anthracene, which is a consequence of its preference for the polar heads and dibenz[a,h]anthracene prefers to be located in the hydrocarbon chain of the phospholipid bilayers. Dibenz[a,h]anthracene and its 3,4-diol-1,2-epoxide may form aggregates in water and lipid phases, and in the water-lipid interface. The implications for the possible effect of dibenz[a,h]anthracene and its 3,4-diol-1,2-epoxide in the lung surfactant phospholipid bilayers are discussed.

  5. Volumetric characterization of ester- and ether-linked lipid bilayers by pressure perturbation calorimetry and densitometry.

    Science.gov (United States)

    Tamai, Nobutake; Nambu, Yuko; Tanaka, Saeko; Goto, Masaki; Matsuki, Hitoshi; Kaneshina, Shoji

    2012-04-01

    We investigated the thermotropic volume behavior of dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC) and dihexadecylphosphatidylcholine (DHPC) membranes using pressure perturbation calorimetry (PPC) and densitometry. The ln φ(2) vs temperature curves (φ(2): apparent molar volume of phospholipid) obtained from the PPC data using an analysis method that we developed agreed with the results from the density measurements for these lipids within the relative difference of about 0.62%. From those curves, the volume changes with the main transition were estimated at 18.0±0.49, 23.5±2.33 and 23.0±0.33 cm(3) mol(-1) for DMPC, DPPC and DHPC, respectively. For DPPC and DMPC, the average volume per methylene group of the hydrocarbon chains v(CH2) calculated by referring to the procedure by Nagle and Wilkinson was consistent with the previous result, which indicates that the DPPC bilayer in the gel state has denser hydrophobic bilayer core than the DMPC bilayer. For DHPC, the volume of the headgroup region v(H) was calculated to be 244 Å(3) by assuming that v(CH2) of DHPC equals that of DPPC above 45°C. This value was comparable to that of DPPC when the volume of the carbonyl groups was considered, which may signify that there is no significant conformational difference in the polar headgroups of both phospholipids. However, it was suggested from the consideration on v(H) of DHPC at 20°C that expansion of the headgroup region should occur as the interdigitated structure is formed, which means some conformational change of the headgroup region is induced by the interdigitation.

  6. Dynamic molecular structure and phase diagram of DPPC-cholesterol binary mixtures: a 2D-ELDOR study.

    Science.gov (United States)

    Chiang, Yun-Wei; Costa-Filho, Antonio J; Freed, Jack H

    2007-09-27

    This paper is an application of 2D electron-electron double resonance (2D-ELDOR) with the "full Sc- method" to study model membranes. We obtain and confirm the phase diagram of 1,2-dipalmitoyl-sn-glycerophosphatidylcholine (DPPC)-cholesterol binary mixtures versus temperature and provide quantitative descriptions for its dynamic molecular structure using 2D-ELDOR at the Ku band. The spectra from the end-chain 16-PC spin label in multilamellar phospholipid vesicles are obtained for cholesterol molar concentrations ranging from 0 to 50% and from 25 to 60 degrees C. This phase diagram consists of liquid-ordered, liquid-disordered, and gel phases and phase coexistence regions. The phase diagram is carefully examined according to the spectroscopic evidence, and the rigorous interpretation for the line shape changes. We show that the 2D-ELDOR spectra differ markedly with variation in the composition. The extensive line shape changes in the 2D-plus-mixing-time representation provide useful information to define and characterize the membrane phases with respect to their dynamic molecular structures and to determine the phase boundaries. The homogeneous T2's are extracted from the pure absorption spectra and are used to further distinguish the membrane phases. These results show 2D-ELDOR to be naturally suitable for probing and reporting the dynamic structures of microdomains in model membrane systems and, moreover, providing a very detailed picture of their molecular dynamic structure, especially with the aid of the "full Sc- method".

  7. Interfacial shear rheology of DPPC under physiologically relevant conditions.

    Science.gov (United States)

    Hermans, Eline; Vermant, Jan

    2014-01-07

    Lipids, and phosphatidylcholines in particular, are major components in cell membranes and in human lung surfactant. Their ability to encapsulate or form stable layers suggests a significant role of the interfacial rheological properties. In the present work we focus on the surface rheological properties of dipalmitoylphosphatidylcholine (DPPC). Literature results are confusing and even contradictory; viscosity values have been reported differ by several orders of magnitude. Moreover, even both purely viscous and gel-like behaviours have been described. Assessing the literature critically, a limited experimental window has been explored correctly, which however does not yet include conditions relevant for the physiological state of DPPC in vivo. A complete temperature and surface pressure analysis of the interfacial shear rheology of DPPC is performed, showing that the monolayer behaves as a viscoelastic liquid with a domain structure. At low frequencies and for a thermally structured monolayer, the interaction of the molecules within the domains can be probed. The low frequency limit of the complex viscosity is measured over a wide range of temperatures and surface pressures. The effects of temperature and surface pressure on the low frequency viscosity can be analysed in terms of the effects of free molecular area. However, at higher frequencies or following a preshear at high shear rates, elasticity becomes important; most probably elasticity due to defects at the edge of the domains in the layer is probed. Preshearing refines the structure and induces more defects. As a result, disagreeing interfacial rheology results in various publications might be due to different pre-treatments of the interface. The obtained dataset and scaling laws enable us to describe the surface viscosity, and its dependence under physiological conditions of DPPC. The implications on functioning of lung surfactants and lung surfactant replacements will be discussed.

  8. Effect of chitosan coating on the characteristics of DPPC liposomes

    Directory of Open Access Journals (Sweden)

    Mohsen M. Mady

    2010-07-01

    Full Text Available Because it is both biocompatible and biodegradable, chitosan has been used to provide a protective capsule in new drug formulations. The present work reports on investigations into some of the physicochemical properties of chitosan-coated liposomes, including drug release rate, transmission electron microscopy (TEM, zeta potential and turbidity measurement. It was found that chitosan increases liposome stability during drug release. The coating of DPPC liposomes with a chitosan layer was confirmed by electron microscopy and the zeta potential of liposomes. The coating of liposomes by chitosan resulted in a marginal increase in the size of the liposomes, adding a layer of (92 ± 27.1 nm. The liposomal zeta potential was found to be increasingly positive as chitosan concentration increased from 0.1% to 0.3% (w/v, before stabilising at a relatively constant value. Turbidity studies revealed that the coating of DPPC liposomes with chitosan did not significantly modify the main phase transition temperature of DPPC at examined chitosan concentrations. The appropriate combination of liposomal and chitosan characteristics may produce liposomes with specific, prolonged and controlled release.

  9. A molecular dynamics model of rhodamine-labeled phospholipid incorporated into a lipid bilayer

    Science.gov (United States)

    Kyrychenko, Alexander

    2010-01-01

    Phospholipids, labeled covalently by a fluorescent dye, are commonly applied in membrane biophysics. In this work, a molecular dynamics model of sulforhodamine attached covalently to a headgroup of 1,2-dipalmitoyl- sn-glycero-3-phosphoethanolamine is developed. It is found that the incorporation of rhodamine-labeled phospholipids into a DPPC bilayer at the low concentration results in small perturbation of the bilayer. In the dye-labeled membrane, the sulforhodamine moiety binds favorably to a polar membrane interface, forming the tilt angle 44° ± 8° to the bilayer normal. The deep location and binding of a bulk sulforhodamine fluorophore lead, therefore, to some 'softening' of the membrane structure.

  10. Structure and fluctuations of a single floating lipid bilayer.

    Science.gov (United States)

    Daillant, J; Bellet-Amalric, E; Braslau, A; Charitat, T; Fragneto, G; Graner, F; Mora, S; Rieutord, F; Stidder, B

    2005-08-16

    A single lipid molecular bilayer of 17 or 18 carbon chain phosphocholines, floating in water near a flat wall, is prepared in the bilayer gel phase and then heated to the fluid phase. Its structure (electron density profile) and height fluctuations are determined by using x-ray reflectivity and non-specular scattering. By fitting the off-specular signal to that calculated for a two-dimensional membrane using a Helfrich Hamiltonian, we determine the three main physical quantities that govern the bilayer height fluctuations: The wall attraction potential is unexpectedly low; the surface tension, roughly independent on chain length and temperature, is moderate (approximately 5 x 10(-4) J.m(-2)) but large enough to dominate the intermediate range of the fluctuation spectrum; and the bending modulus abruptly decreases by an order-of-magnitude from 10(-18) J to 10(-19) J at the bilayer gel-to-fluid transition.

  11. Advances in the application of food emulsifier α-gel phases: Saturated monoglycerides, polyglycerol fatty acid esters, and their derivatives.

    Science.gov (United States)

    Wang, Fan C; Marangoni, Alejandro G

    2016-12-01

    Emulsifiers form complex structures in colloidal systems. One of these structures, the α-gel phase, has drawn much research interest. α-gel phases are formed by emulsifiers that are stable in the α-crystalline structure in the presence of water. The α-gel phase has shown superior functionality in a variety of applications because it has a water-rich lamellar structure. Even though studies on emulsifier α-gel phases emerged over half a century ago, there is still a knowledge gap on fundamental properties of α-gel phases formed by a variety of emulsifiers. This article summarizes recent studies on the physical and chemical properties of α-gel phases formed by several food emulsifiers, specifically saturated monoglycerides, polyglycerol monoester and diesters of fatty acid, and sodium stearoyl lactylate. Recent research has advanced the understanding of factors affecting the stability and foamability of the α-gel phases. Current and potential applications of α-gel phases in baked food products and in personal care products are also reviewed here.

  12. Fluctuations in lipid bilayers: Are they understood?

    CERN Document Server

    Schmid, Friederike

    2013-01-01

    We review recent computer simulation studies of undulating lipid bilayers. Theoretical interpretations of such fluctuating membranes are most commonly based on generalized Helfrich-type elastic models, with additional contributions of local "protrusions" and/or density fluctuations. Such models provide an excellent basis for describing the fluctuations of tensionless bilayers in the fluid phase at a quantitative level. However, this description is found to fail for membranes in the gel phase and for membranes subject to high tensions. The fluctuations of tilted gel membranes show a signature of the modulated ripple structure, which is a nearby phase observed in the pretransition regime between the fluid and tilted gel state. This complicates a quantitative analysis on mesoscopic length scales. In the case of fluid membranes under tension, the large-wavelength fluctuation modes are found to be significantly softer than predicted by theory. In the latter context, we also address the general problem of the relat...

  13. Phase equilibria in DOPC/DPPC-d62/cholesterol mixtures.

    Science.gov (United States)

    Davis, James H; Clair, Jesse James; Juhasz, Janos

    2009-01-01

    There is broad interest in the question of fluid-fluid phase coexistence in membranes, in particular, whether evidence for liquid-disordered (l(d))-liquid-ordered (l(o)) two-phase regions or membrane "rafts" can be found in natural membranes. In model membrane systems, such phase behavior is observed, and we have used deuterium nuclear magnetic resonance spectroscopy to map the phase boundaries of ternary mixtures containing 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), chain-perdeuterated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC-d(62)), and cholesterol. For both this ternary model system and the binary DPPC-d(62)/cholesterol system, we present clear evidence for l(d)-l(o) two-phase coexistence. We have selected sample compositions to focus on this region of fluid-fluid phase coexistence and to determine its temperature and composition ranges. The deuterium nuclear magnetic resonance spectra for compositions near the l(d)-l(o) phase boundary at high cholesterol concentrations show evidence of exchange broadening or critical fluctuations in composition, similar to that reported by Vist and Davis. There appears to be a line of critical compositions ranging from 48 degrees C for a DOPC/DPPC-d(62)/cholesterol composition of 0:75:25, to approximately -8 degrees C for the composition 57:14:29. At temperatures below this two-phase region, there is a region of three-phase coexistence (l(d)-l(o)-gel). These results are collected and presented in terms of a partial ternary phase diagram that is consistent with previously reported results of Vist and Davis.

  14. Thermotropic and barotropic phase transitions on diacylphosphatidylethanolamine bilayer membranes.

    Science.gov (United States)

    Matsuki, Hitoshi; Endo, Shigeru; Sueyoshi, Ryosuke; Goto, Masaki; Tamai, Nobutake; Kaneshina, Shoji

    2017-07-01

    The bilayer phase transitions of four diacylphosphatidylethanolamines (PEs) with matched saturated acyl chains (Cn=12, 14, 16 and 18) and two PEs with matched unsaturated acyl chains containing a different kind of double bonds were observed by differential scanning calorimetry under atmospheric pressure and light-transmittance measurements under high pressure. The temperature-pressure phase diagrams for these PE bilayer membranes were constructed from the obtained phase-transition data. The saturated PE bilayer membranes underwent two different phase transitions related to the liquid crystalline (Lα) phase, the transition from the hydrated crystalline (Lc) phase and the chain melting (gel (Lβ) to Lα) transition, depending on the thermal history. Pressure altered the gel-phase stability of the bilayer membranes of PEs with longer chains at a low pressure. Comparing the thermodynamic quantities of the saturated PE bilayer membranes with those of diacylphosphatidylcholine (PC) bilayer membranes, the PE bilayer membranes showed higher phase-transition temperatures and formed more stable Lc phase, which originates from the strong interaction between polar head groups of PE molecules. On the other hand, the unsaturated PE bilayer membranes underwent the transition from the Lα phase to the inverted hexagonal (HII) phase at a high temperature and this transition showed a small transition enthalpy but high pressure-responsivity. It turned out that the kind of double bonds markedly affects both bilayer-bilayer and bilayer-nonbilayer transitions and the Lα/HII transition is a volume driven transition for the reconstruction of molecular packing. Further, the phase-transition behavior was explained by chemical potential curves of bilayer phases. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Probing the position of resveratrol in lipid bilayers

    DEFF Research Database (Denmark)

    de Ghellinck, Alexis; Shen, Chen; Fragneto, Giovanna

    2015-01-01

    The effect of the natural antioxidant resveratrol on the structure of solid supported di-palmitoyl-phosphatidyl-choline (DPPC) bilayers in their fluid state was investigated by neutron reflectometry. Results reveal an accumulation of resveratrol (up to 25%, mol/mol) inside the headgroups...... and they exclude its presence in the hydrophobic core. The presence of resveratrol induces an increase of the average thickness and of the interfacial roughness of the headgroup layer. This may be due to a change of the tilt angle of the phosphocholine headgroups residing next to the resveratrol to a more upright...... orientation and leading to a reduction of the projected area per headgroup. This effect is propagated into the hydrophobic core, where the chain packing is modified despite the absence of resveratrol. When interacting with a DPPC/cholesterol membrane, resveratrol has a similar effect on the neighboring PC...

  16. Sol-gel composite material characteristics caused by different dielectric constant sol-gel phases

    Science.gov (United States)

    Kimoto, Keisuke; Matsumoto, Makoto; Kaneko, Tsukasa; Kobayashi, Makiko

    2016-07-01

    Ultrasonic transducers prepared by a sol-gel composite method have been investigated in the field of nondestructive testing (NDT). Sol-gel composite materials could be ideal piezoelectric materials for ultrasonic transducer applications in the NDT field, and a new sol-gel composite with desirable characteristics has been developed. Three kinds of sol-gel composite materials composed of different dielectric constant sol-gel phases, Pb(Zr,Ti)O3 (PZT), Bi4Ti3O12 (BiT), and BaTiO3 (BT), and the same piezoelectric powder phase, PbTiO3 (PT), were fabricated and their properties were compared quantitatively. As a result, the PT/BT, sol-gel composite with the highest dielectric constant sol-gel phase showed the highest d 33 and signal strength. In addition, only PT/BT was successfully poled by room-temperature corona poling with reasonable signal strength.

  17. Strong influence of periodic boundary conditions on lateral diffusion in lipid bilayer membranes

    Energy Technology Data Exchange (ETDEWEB)

    Camley, Brian A. [Center for Theoretical Biological Physics and Department of Physics, University of California, San Diego, California 92093 (United States); Department of Physics, University of California, Santa Barbara, California 93106 (United States); Lerner, Michael G. [Department of Physics and Astronomy, Earlham College, Richmond, Indiana 47374 (United States); Laboratory of Computational Biology, National Heart, Lung, and Blood Institute, National Institutes of Health, Bethesda, Maryland 20892 (United States); Pastor, Richard W. [Laboratory of Computational Biology, National Heart, Lung, and Blood Institute, National Institutes of Health, Bethesda, Maryland 20892 (United States); Brown, Frank L. H. [Department of Physics, University of California, Santa Barbara, California 93106 (United States); Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106 (United States)

    2015-12-28

    The Saffman-Delbrück hydrodynamic model for lipid-bilayer membranes is modified to account for the periodic boundary conditions commonly imposed in molecular simulations. Predicted lateral diffusion coefficients for membrane-embedded solid bodies are sensitive to box shape and converge slowly to the limit of infinite box size, raising serious doubts for the prospects of using detailed simulations to accurately predict membrane-protein diffusivities and related transport properties. Estimates for the relative error associated with periodic boundary artifacts are 50% and higher for fully atomistic models in currently feasible simulation boxes. MARTINI simulations of LacY membrane protein diffusion and LacY dimer diffusion in DPPC membranes and lipid diffusion in pure DPPC bilayers support the underlying hydrodynamic model.

  18. Reparameterization of all-atom dipalmitoylphosphatidylcholine lipid parameters enables simulation of fluid bilayers at zero tension

    DEFF Research Database (Denmark)

    Sonne, Jacob; Jensen, M.Ø.; Hansen, Flemming Yssing;

    2007-01-01

    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...... fluid phase of DPPC bilayers can now be simulated in all-atom simulations in the NPT ensemble by employing our modified CHARMM27 force field....

  19. Strong influence of periodic boundary conditions on lateral diffusion in lipid bilayer membranes

    Science.gov (United States)

    Camley, Brian A.; Lerner, Michael G.; Pastor, Richard W.; Brown, Frank L. H.

    2015-12-01

    The Saffman-Delbrück hydrodynamic model for lipid-bilayer membranes is modified to account for the periodic boundary conditions commonly imposed in molecular simulations. Predicted lateral diffusion coefficients for membrane-embedded solid bodies are sensitive to box shape and converge slowly to the limit of infinite box size, raising serious doubts for the prospects of using detailed simulations to accurately predict membrane-protein diffusivities and related transport properties. Estimates for the relative error associated with periodic boundary artifacts are 50% and higher for fully atomistic models in currently feasible simulation boxes. MARTINI simulations of LacY membrane protein diffusion and LacY dimer diffusion in DPPC membranes and lipid diffusion in pure DPPC bilayers support the underlying hydrodynamic model.

  20. Fluorescence depolarization analysis of thermal phase transition in DPPC and DMPG aqueous dispersions

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Amando Siuiti, E-mail: amandosi@ffclrp.usp.br; Rodrigues, Ana Paula; Moreira Pazin, Wallance; Berardi Barioni, Marina

    2015-02-15

    We performed an overall analysis of steady state, kinetic and dynamical parameters of phospholipids labeled with 7-nitrobenz-2-oxa-1,3-diazol-4-yl (NBD), to investigate the structural changes accompanying the phase transition of dimyristoyl phosphatidylglycerol (DMPG) vesicles, under low and high ionic strength conditions. For comparison, we also performed experiments on dimyristoyl phosphatidylcholine (DPPC) vesicles, which exhibit a well-defined thermal phase transition. Fluorescence parameters alone (lifetime, pre-exponential factor, rotational correlation times, and initial anisotropy) do not describe the thermal behavior of the vesicles. Combination of intensity decay and anisotropy decay data allows the calculation of mean anisotropy values, and among the several parameters obtained from time-resolved measurements, the main contribution to the mean anisotropy comes from the residual anisotropy, obtained as the limit value at long times. The results of calculations were comparable to the steady state measurements, and allowed the observation of the dependence between the thermal phase transition in DMPG and the ionic strength of the medium. The presence of NaCl affects the lipid packing leading to structural constraints onto the probes that are systematically higher than those observed in low ionic strength. In low ionic strength the long rotational correlation time of the NBD-PE (NBD-phosphatidylethanolamine) probe presents peculiar behavior, showing transient changes along the broad gel–fluid transition, that occurs parallel to the modifications in the scattering intensity. - Highlights: • Time-resolved data were combined to calculate mean values of fluorescence anisotropy. • Fluorescence structural parameters describe lipid vesicles thermal phase transition. • Calculated fluorescence anisotropy describes ionic strength effects in DMPG bilayers.

  1. Strong Static Magnetic Fields Increase the Gel Signal in Partially Hydrated DPPC/DMPC Membranes

    Directory of Open Access Journals (Sweden)

    Jennifer Tang

    2015-09-01

    Full Text Available NIt was recently reported that static magnetic fields increase lipid order in the hydrophobic membrane core of dehydrated native plant plasma membranes [Poinapen, Soft Matter 9:6804-6813, 2013]. As plasma membranes are multicomponent, highly complex structures, in order to elucidate the origin of this effect, we prepared model membranes consisting of a lipid species with low and high melting temperature. By controlling the temperature, bilayers coexisting of small gel and fluid domains were prepared as a basic model for the plasma membrane core. We studied molecular order in mixed lipid membranes made of dimyristoyl-sn-glycero-3-phosphocholine (DMPC and dipalmitoyl-sn-glycero-3-phosphocholine (DPPC using neutron diffraction in the presence of strong static magnetic fields up to 3.5 T. The contribution of the hydrophobic membrane core was highlighted through deuterium labeling the lipid acyl chains. There was no observable effect on lipid organization in fluid or gel domains at high hydration of the membranes. However, lipid order was found to be enhanced at a reduced relative humidity of 43%: a magnetic field of 3.5 T led to an increase of the gel signal in the diffraction patterns of 5%. While all biological materials have weak diamagnetic properties, the corresponding energy is too small to compete against thermal disorder or viscous effects in the case of lipid molecules. We tentatively propose that the interaction between the fatty acid chains’ electric moment and the external magnetic field is driving the lipid tails in the hydrophobic membrane core into a better ordered state.

  2. AN EXPERIMENTAL STUDY ON THE SOL/GEL PHASE TRANSITION OF LINEAR POLYMER IN THE PRESENCE OF CROSSLINKERS

    Institute of Scientific and Technical Information of China (English)

    HAN Ming; SHI Lianghe; YE Meiling; MULLER Guy

    1996-01-01

    The sol/gel phase diagrams were studied for two systems: polyacrylamide/Cr (Ⅲ) and polyacrylamide/glyoxal. Sol or gel phase could be distinguished according to the concentrations of polymer and crosslinker. The boundary polymer concentration did not depend on the types of gelation and decreased with increasing polymer dimension (molecular weight and conformation). The gelation, which is basically interchain bonding, requires the occurrence of entanglement. The overlap concentration is thus considered as the minimum polymer concentration required for gelation.

  3. Refined OPLS All-Atom Force Field for Saturated Phosphatidylcholine Bilayers at Full Hydration

    DEFF Research Database (Denmark)

    Maciejewski, A.; Pasenkiewicz-Gierula, M.; Cramariuc, O.

    2014-01-01

    . In the present study, we determined the parameters for torsion angles in the phosphatidylcholine and glycerol moieties and in the acyl chains, as well the partial atomic charges. In these calculations, we used three methods: (1) Hartree-Fock (HF), (2) second order Moller-Plesset perturbation theory (MP2), and (3...... one was found to be able to satisfactorily reproduce experimental data for the lipid bilayer. The successful DPPC model was obtained from MP2 calculations in an implicit polar environment (PCM)....

  4. Photoinduced electron transfer of chlorophyll in lipid bilayer system

    Indian Academy of Sciences (India)

    D K Lee; K W Seo; Y S Kang

    2002-12-01

    Photoinduced electron transfer from chlorophyll- through the interface of dipalmitoylphosphatidylcholine (DPPC) headgroup of the lipid bilayers was studied with electron magnetic resonance (EMR). The photoproduced radicals were identified with electron spin resonance (ESR) and radical yields of chlorophyll- were determined by double integration ESR spectra. The formation of vesicles was identified by changes in measured max values from diethyl ether solutions to vesicles solutions indirectly, and observed directly with SEM and TEM images. The efficiency of photosynthesis in model system was determined by measuring the amount of chlorophyll-a radical yields which were obtained from integration of ESR spectra.

  5. Infrared intensity of 1-monolaurin-water systems in the gel phase

    Science.gov (United States)

    Kanesaka, Isao; Ishizaka, Makiko; Shimizu, Kunihiko

    2000-11-01

    The infrared spectra of 1-monolaurin-water systems, where KSCN is added as the intensity standard, were observed and the infrared intensity of the bands due to acyl groups measured relatively to that of the CN stretching. The infrared intensities of the bands parallel and perpendicular to the paraffin chains decrease and increase, respectively, on going from the crystalline β phase to the gel phase, confirming that these intensity changes result from the long-range interaction among oscillating dipoles. The infrared spectra with no CH 2 rocking and the splitting of the CH 2 rocking are also discussed with the same interaction model.

  6. Rheological model for sol-gel phase transition of thermo-aged heavy oil fractions

    Directory of Open Access Journals (Sweden)

    Xiomara Andrea Vargas Arenas

    2010-05-01

    Full Text Available A power-law rheological model is proposed in this paper: G’’ (ω ∼ ωn and G’ (ω ~ ωn. It represents the increased connectivity between thermo-aged asphalt molecules in a rheo-reactor as one of the applications of systematic rheology. The results confirmed a sol-gel phase transition tendency for aged asphalt in the experimental frequency window at temperatures below 40°C. Such pattern could have been related to the structuring effect arising from the thermo-oxidative asphalt aging process during continuous agitation which has been suitably described by the micellar model of asphalt.

  7. Predicting proton titration in cationic micelle and bilayer environments

    Energy Technology Data Exchange (ETDEWEB)

    Morrow, Brian H.; Shen, Jana K. [Department of Pharmaceutical Sciences, University of Maryland, Baltimore, Maryland 21201 (United States); Eike, David M.; Murch, Bruce P.; Koenig, Peter H. [Computational Chemistry, Modeling and Simulation GCO, Procter and Gamble, Cincinnati, Ohio 45201 (United States)

    2014-08-28

    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 in 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.

  8. The GM1 Ganglioside Forms GM1-Rich Gel Phase Microdomains within Lipid Rafts

    Directory of Open Access Journals (Sweden)

    Lucia Becucci

    2014-07-01

    Full Text Available Mercury-supported, self-assembled monolayers (SAMs of the sole dioleoylphosphatidylcholine (DOPC and of a raft-forming mixture of DOPC, cholesterol (Chol and palmitoylsphingomyelin (PSM of (59:26:15 mol% composition, were investigated by electrochemical impedance spectroscopy (EIS, both in the absence and in the presence of the monosialoganglioside GM1. The impedance spectra of these four SAMs were fitted by a series of parallel combinations of a resistance and a capacitance (RC meshes and displayed on plots of ωZ′ against −ωZ″, where Z′ and Z″ are the in-phase and quadrature components of the impedance and ω is the angular frequency. A comparison among these different impedance spectra points to the formation of GM1-rich gel phase microdomains within the lipid rafts of the DOPC/Chol/PSM mixture, thanks to the unique molecular-level smooth support provided by mercury, which allows EIS to detect the protruding gel phase microdomains by averaging them over a macroscopically large area.

  9. Topologies, structures and parameter files for lipid simulations in GROMACS with the OPLS-aa force field: DPPC, POPC, DOPC, PEPC, and cholesterol

    Directory of Open Access Journals (Sweden)

    Waldemar Kulig

    2015-12-01

    Full Text Available In this data article we provide topologies and force field parameters files for molecular dynamics simulations of lipids in the OPLS-aa force field using the GROMACS package. This is the first systematic parameterization of lipid molecules in this force field. Topologies are provided for four phosphatidylcholines: saturated DPPC, mono-cis unsaturated POPC and DOPC, and mono-trans unsaturated PEPC. Parameterization of the phosphatidylcholines was achieved in two steps: first, we supplemented the OPLS force field parameters for DPPC with new parameters for torsion angles and van der Waals parameters for the carbon and hydrogen atoms in the acyl chains, as well as new partial atomic charges and parameters for torsion angles in the phosphatidylcholine and glycerol moieties [1]. Next, we derived parameters for the cis and trans double bonds and the neighboring them single bonds [2]. Additionally, we provide GROMACS input files with parameters describing simulation conditions (md.mdp, which are strongly recommended to be used with these lipids models. The data are associated with the research article “Cis and trans unsaturated phosphatidylcholine bilayers: a molecular dynamics simulation study” [2] and provided as supporting materials.

  10. Organic salts and aromatic substrates in two-component gel phase formation: the study of properties and release processes.

    Science.gov (United States)

    Vitale, Paola; D'Anna, Francesca; Marullo, Salvatore; Noto, Renato

    2015-09-07

    To identify gel phases able to act as confined reaction media or materials for the removal of organic pollutants, we studied two-component gel phases formed by naphthalenedisulfonate diimidazolium salts in the presence of some organic guests, in 1-propanol solution. Guests differing in π-surface area, bulkiness and electronic properties were taken into account. Soft materials obtained were investigated for their thermal stability, self-repairing ability and morphology. Furthermore, two-component gel phase formation was studied using resonance light scattering (RLS) measurements. Guest release processes from the gel phase were also studied. These processes were monitored as a function of time using both UV-vis and RLS measurements and considering important parameters such as the gelator concentration, the nature of extraction solvent and the extension of contact surface area between solvent and gel phase. Data collected shed light on the properties of the two-component gels and could represent a useful tool to better plan the application of these soft materials.

  11. Dynamics and stability of lipid bilayers modulated by thermosensitive polypeptides, cholesterols, and PEGylated lipids.

    Science.gov (United States)

    Lee, Hwankyu; Kim, Hyun Ryoung; Park, Jae Chan

    2014-02-28

    Lipid bilayers, which consist of dipalmitoylglycerophosphocholines (DPPCs), PEGylated lipids, cholesterols, and elastin-like polypeptides (ELPs; [VPGVG]3) at different molar ratios, were simulated. Simulations were carried out for 2 μs using the coarse-grained (CG) model that had captured the experimentally observed phase behavior of PEGylated lipids and lateral diffusivity of DPPC bilayers. Starting with the initial position of ELPs on the bilayer surface, ELPs insert into the hydrophobic region of the bilayer because of their interaction with lipid tails, consistent with previous all-atom simulations. Lateral diffusion coefficients of DPPCs significantly increase in the bilayer composed of more ELPs and less cholesterols, showing their opposite effects on the bilayer dynamics. In particular, ELPs modulate the dynamics and phase for the disordered liquid bilayer, but not for the ordered gel bilayer, indicating that ELPs can destabilize only the disordered bilayer. In the ordered bilayer, ELP chains tend to have a spherical shape and slowly diffuse, while they are extended and diffuse faster in the disordered bilayer, indicating the effect of the bilayer phase on the conformation and diffusivity of ELPs. These findings explain the experimental observation that the ELP-conjugated liposomes are stable at 310 K (ordered phase) but become unstable and release the encapsulated drugs at 315 K (disordered phase), which suggests the effects of ELPs and cholesterols. Since the cholesterol-stabilized bilayer can be destabilized by the extended shaped ELPs only in the disordered phase (not in the ordered phase), the inclusion of cholesterols is required to safely shield drugs at 310 K as well as allow ELPs to disrupt lipids and destabilize the liposomes at 315 K.

  12. Compositional and structural characterization of monolayers and bilayers composed of native pulmonary surfactant from wild type mice

    DEFF Research Database (Denmark)

    Bernardino de la Serna, Jorge; Hansen, Soren; Berzina, Zane

    2013-01-01

    This work comprises a structural and dynamical study of monolayers and bilayers composed of native pulmonary surfactant from mice. Spatially resolved information was obtained using fluorescence (confocal, wide field and two photon excitation) and atomic force microscopy methods. Lipid mass...... spectrometry experiments were also performed in order to obtain relevant information on the lipid composition of this material. Bilayers composed of mice pulmonary surfactant showed coexistence of distinct domains at room temperature, with morphologies and lateral packing resembling the coexistence of liquid...... ordered (lo)/liquid disordered (ld)-like phases reported previously in porcine lung surfactant. Interestingly, the molar ratio of saturated (mostly DPPC)/non-saturated phospholipid species and cholesterol measured in the innate material corresponds with that of a DOPC/DPPC/cholesterol mixture showing lo...

  13. Temperature-controlled structure and kinetics of ripple phases in one- and two-component supported lipid bilayers

    DEFF Research Database (Denmark)

    Kaasgaard, Thomas; Leidy, Chad; Crowe, J.H.

    2003-01-01

    ripples was seen. From height profiles of the AFM images, estimates of the amplitudes of the different ripple phases are reported. To elucidate the processes of ripple formation and disappearance, a ripple-phase DPPC lipid bilayer was taken through the pretransition in the cooling and the heating...... was heated from the ripple phase and into the ripple-phase/fluid-phase coexistence temperature region, the AFM images revealed that several dynamic properties of the ripple phase are important for the melting behavior of the lipid mixture. Onset of melting is observed at grain boundaries between different......Temperature-controlled atomic force microscopy (AFM) has been used to visualize and study the structure and kinetics of ripple phases in one-component dipalmitoylphosphaticlylcholine (DPPC) and two-component dimyristoylphosphatidylcholine-distearoylphosphatidylcholine (DMPC-DSPC) lipid bilayers...

  14. Depth profiles of pulmonary surfactant protein B in phosphatidylcholine bilayers, studied by fluorescence and electron spin resonance spectroscopy

    DEFF Research Database (Denmark)

    Cruz, A; Casals, C; Plasencia, I

    1998-01-01

    . These differences in the extent of insertion lead to qualitative and quantitative differences in the effect of the protein on the mobility of the phospholipid acyl chains, as studied by spin-label electron spin resonance (ESR) spectroscopy, and could represent different functional stages in the surfactant cycle......Pulmonary surfactant-associated protein B (SP-B) has been isolated from porcine lungs and reconstituted in bilayers of dipalmitoylphosphatidylcholine (DPPC) or egg yolk phosphatidylcholine (PC) to characterize the extent of insertion of the protein into phospholipid bilayers. The parameters...... for the interaction of SP-B with DPPC or PC using different reconstitution protocols have been estimated from the changes induced in the fluorescence emission spectrum of the single protein tryptophan. All the different reconstituted SP-B-phospholipid preparations studied had similar Kd values for the binding...

  15. Lipid-assisted formation and dispersion of aqueous and bilayer-embedded nano-C60.

    Science.gov (United States)

    Chen, Yanjing; Bothun, Geoffrey D

    2009-05-05

    Lipid assemblies provide a biocompatible approach for preparing aqueous nanoparticles. In this work, dipalmitoylphosphatidylcholine (DPPC) was used to assist in the formation and dispersion of C(60) and nano-C(60) aggregates using a modified reverse phase evaporation (REV) method. This method led to the rapid formation of aqueous nano-C(60) at DPPC/C(60) molar ratios from 500:1 to 100:1 (12-38 nm; verified by cryogenic transmission electron microscopy), which were present in the bulk phase and encapsulated within vesicles. In addition to forming nanoparticles, C(60) was trapped within the vesicle bilayer and led to a reduction in the lipid melting temperature. Solvent extraction was used to isolate nano-C(60) from the lipids and bilayer-embedded C(60). Our results suggest that bilayer-embedded C(60) was present as molecular C(60) and as small amorphous nano-C(60) (2.3 +/- 0.4 nm), which clustered in the aqueous phase after the lipids were extracted. In addition to developing a new technique for nano-C(60) formation, our results suggest that the lipid bilayer may be used as a hydrophobic region for dispersing and assembling small nano-C(60).

  16. Effects of pentanol isomers on the phase behavior of phospholipid bilayer membranes.

    Science.gov (United States)

    Griffin, Kathryn L; Cheng, Chih-Yin; Smith, Eric A; Dea, Phoebe K

    2010-11-01

    Differential scanning calorimetry (DSC) was used to analyze the thermotropic phase behavior of dipalmitoylphosphatidylcholine (DPPC) bilayers in the presence of pentanol isomers. The concentration of each pentanol isomer needed to induce the interdigitated phase was determined by the appearance of a biphasic effect in the main transition temperatures, the onset of a hysteresis associated with the main transition from the gel-to-liquid crystalline phase, and the disappearance of the pretransition. Lower threshold concentrations were found to correlate with isomers of greater alkyl chain length while branching of the alkyl chain was found to increase biphasic behavior. The addition of a methyl group to butanol systems drastically decreased threshold concentrations. However, as demonstrated in the DPPC/neopentanol system, branching of the alkyl chain away from the -OH group lowers the threshold concentration while maintaining a biphasic effect.

  17. Responsive Gel-Gel Phase Transitions in Artificially Engineered Protein Hydrogels

    Science.gov (United States)

    Olsen, B. D.

    2012-02-01

    Artificially engineered protein hydrogels provide an attractive platform for biomedical materials due to their similarity to components of the native extracellular matrix. Engineering responsive transitions between shear-thinning and tough gel phases in these materials could potentially enable gels that are both shear-thinning and tough to be produced as novel injectable biomaterials. To engineer a gel with such transitions, a triblock copolymer with thermoresponsive polymer endblocks and an artificially engineered protein gel midblock is designed. Temperature is used to trigger a transition from a single network protein hydrogel phase to a double network phase with both protein and block copolymer networks present at different length scales. The thermodynamics of network formation and resulting structural changes are established using small-angle scattering, birefringence, and dynamic scanning calorimetry. The formation of the second network is shown to produce a large, nonlinear increase in the elastic modulus as well as enhancements in creep compliance and toughness. Although the gels show yielding behavior in both the single and double network regimes, a qualitative change in the deformation mechanism is observed due to the structural changes.

  18. Molecular Dynamics Simulation of Water Pore Formation in Lipid Bilayer Induced by Shock Waves

    Science.gov (United States)

    Koshiyama, Ken-ichiro; Kodama, Tetsuya; Yano, Takeru; Fujikawa, Shigeo

    2006-05-01

    Water molecule penetration into a bilayer hydrophobic region with a shock wave impulse has been investigated using molecular dynamics simulations [Koshiyama et al., AIP Conference Proceedings, 754, 104-106, (2005)]. Here we report results of simulation of spontaneous water pore formation in a bilayer that contains water molecules in the hydrophobic region in an initial state. The bilayers of 128 DPPC lipid and 3655 water molecules with insertion of 392, 784, and 1176 water molecules in the hydrophobic region are simulated. A water pore is spontaneously formed when 1176 water molecules exist in the hydrophobic region. The water pore diameter is estimated to be c.a. 1.9 nm, which is three times larger than that of 5-fluorouracil (5FU) used in cancer treatment.

  19. Lipid bilayers and interfaces

    NARCIS (Netherlands)

    Kik, R.A.

    2007-01-01

    In biological systems lipid bilayers are subject to many different interactions with other entities. These can range from proteins that are attached to the hydrophilic region of the bilayer or transmembrane proteins that interact with the hydrophobic region of the lipid bilayer. Interaction between

  20. Multi-Stacked Supported Lipid Bilayer Micropatterning through Polymer Stencil Lift-Off

    Directory of Open Access Journals (Sweden)

    Yujie Zhu

    2015-08-01

    Full Text Available Complex multi-lamellar structures play a critical role in biological systems, where they are present as lamellar bodies, and as part of biological assemblies that control energy transduction processes. Multi-lamellar lipid layers not only provide interesting systems for fundamental research on membrane structure and bilayer-associated polypeptides, but can also serve as components in bioinspired materials or devices. Although the ability to pattern stacked lipid bilayers at the micron scale is of importance for these purposes, limited work has been done in developing such patterning techniques. Here, we present a simple and direct approach to pattern stacked supported lipid bilayers (SLBs using polymer stencil lift-off and the electrostatic interactions between cationic and anionic lipids. Both homogeneous and phase-segregated stacked SLB patterns were produced, demonstrating that the stacked lipid bilayers retain lateral diffusivity. We demonstrate patterned SLB stacks of up to four bilayers, where fluorescence resonance energy transfer (FRET and quenching was used to probe the interactions between lipid bilayers. Furthermore, the study of lipid phase behaviour showed that gel phase domains align between adjacent layers. The proposed stacked SLB pattern platform provides a robust model for studying lipid behaviour with a controlled number of bilayers, and an attractive means towards building functional bioinspired materials or devices.

  1. Corrugation of Phase-Separated Lipid Bilayers Supported by Nanoporous Silica Xerogel Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Goksu, E I; Nellis, B A; Lin, W; Satcher Jr., J H; Groves, J T; Risbud, S H; Longo, M L

    2008-10-30

    Lipid bilayers supported by substrates with nanometer-scale surface corrugations holds interest in understanding both nanoparticle-membrane interactions and the challenges of constructing models of cell membranes on surfaces with desirable properties, e.g. porosity. Here, we successfully form a two-phase (gel-fluid) lipid bilayer supported by nanoporous silica xerogel. Surface topology, diffusion, and lipid density in comparison to mica-supported lipid bilayers were characterized by AFM, FRAP, FCS, and quantitative fluorescence microscopy, respectively. We found that the two-phase lipid bilayer follows the xerogel surface contours. The corrugation imparted on the lipid bilayer results in a lipid density that is twice that on a flat mica surface. In direct agreement with the doubling of actual bilayer area in a projected area, we find that the lateral diffusion coefficient (D) of lipids on xerogel ({approx}1.7 {micro}m{sup 2}/s) is predictably lower than on mica ({approx}4.1 {micro}m{sup 2}/s) by both FRAP and FCS techniques. Furthermore, the gel-phase domains on xerogel compared to mica were larger and less numerous. Overall, our results suggest the presence of a relatively defect-free continuous two-phase bilayer that penetrates approximately midway into the first layer of {approx}50 nm xerogel beads.

  2. Interplay between alkyl chain asymmetry and cholesterol addition in the rigid ion pair amphiphile bilayer systems

    Science.gov (United States)

    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.

  3. Effect of gamma irradiation on hyaluronic acid and dipalmitoylphosphatidylcholine (DPPC) interaction

    Science.gov (United States)

    Ahmad, Ainee Fatimah; Mohd, Hur Munawar Kabir; bin Ayob, Muhammad Taqiyuddin Mawardi; Rosli, Nur Ratasha Alia Md; Mohamed, Faizal; Radiman, Shahidan; Rahman, Irman Abdul

    2014-09-01

    DPPC lipids are the major component constituting the biological membrane, and their importances in various physiological functions are well documented. Hyaluronic acid (HA) in the synovial joint fluid functions as a lubricant, shock absorber and a nutrient carrier. Gamma irradiation has also been found to be effective in depolymerizing and cleaving molecular chains related to free radicals, thus extends with changes in chemical composition as well as its physiological functions. This research are conducted to investigate the hyaluronic acid (HA) and 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) interaction in form of vesicles and its effect to gamma radiation. The size of DPPC vesicles formed via gentle hydration method is between 100 to 200 nm in diameter. HA (0.1, 0.5 and 1.0 mg/ml) was added into the vesicles and characterized by using TEM to determine vesicle size distributions, fusion and rupture of DPPC structure. The results demonstrated that the size of the vesicles approximately between 200 to 300 nm which caused by vesicles fusion with HA and formed even larger vesicles. After being irradiated by 0 to 200 Gy, the size of vesicles decreased as HA was degraded. To elucidate the mechanism of these effects, FTIR spectra were carried out and have shown that at absorption bands at 1700-1750 cm-1 due to formation of carboxylic acid and leads to alteration of HA structure.

  4. Effect of gamma irradiation on hyaluronic acid and dipalmitoylphosphatidylcholine (DPPC) interaction

    Energy Technology Data Exchange (ETDEWEB)

    Ahmad, Ainee Fatimah; Mohd, Hur Munawar Kabir; Taqiyuddin Mawardi bin Ayob, Muhammad; Rosli, Nur Ratasha Alia Md; Mohamed, Faizal; Radiman, Shahidan; Rahman, Irman Abdul [School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia)

    2014-09-03

    DPPC lipids are the major component constituting the biological membrane, and their importances in various physiological functions are well documented. Hyaluronic acid (HA) in the synovial joint fluid functions as a lubricant, shock absorber and a nutrient carrier. Gamma irradiation has also been found to be effective in depolymerizing and cleaving molecular chains related to free radicals, thus extends with changes in chemical composition as well as its physiological functions. This research are conducted to investigate the hyaluronic acid (HA) and 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) interaction in form of vesicles and its effect to gamma radiation. The size of DPPC vesicles formed via gentle hydration method is between 100 to 200 nm in diameter. HA (0.1, 0.5 and 1.0 mg/ml) was added into the vesicles and characterized by using TEM to determine vesicle size distributions, fusion and rupture of DPPC structure. The results demonstrated that the size of the vesicles approximately between 200 to 300 nm which caused by vesicles fusion with HA and formed even larger vesicles. After being irradiated by 0 to 200 Gy, the size of vesicles decreased as HA was degraded. To elucidate the mechanism of these effects, FTIR spectra were carried out and have shown that at absorption bands at 1700–1750 cm{sup −1} due to formation of carboxylic acid and leads to alteration of HA structure.

  5. Surface properties and morphology of mixed POSS-DPPC monolayers at the air/water interface.

    Science.gov (United States)

    Rojewska, Monika; Skrzypiec, Marta; Prochaska, Krystyna

    2017-02-01

    From the point of view of the possible medical applications of POSS (polyhedral oligomeric silsesquioxanes), it is crucial to analyse interactions occurring between POSS and model biological membrane at molecular level. Knowledge of the interaction between POSS and DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) allows prediction of the impact of POSS contained in biomaterials or cosmetics on a living organism. In the study presented, the surface properties and morphology of Langmuir monolayers formed by mixtures of POSS and the phospholipid (DPPC) at the air/water surface are examined. We selected two POSS derivatives, with completely different chemical structure of substituents attached to the corner of the silicon open cage, which allowed the analysis of the impact of the character of organic moieties (strongly hydrophobic or clearly hydrophilic) on the order of POSS molecules and their tendency to form self-aggregates at the air/water surface. POSS derivatives significantly changed the profile of the π-A isotherms obtained for DPPC but in different ways. On the basis of the regular solution theory, the miscibility and stability of the two components in the monolayer were analysed in terms of compression modulus (Cs(-1)), excess Gibbs free energy (ΔGexc), activity coefficients (γ) and interaction parameter (ξ). The results obtained indicate the existence of two different interaction mechanisms between DPPC and POSS which depend on the chemical character of moieties present in POSS molecules.

  6. Formation of ring calcium oxalate patterns induced by domains in DPPC Langmuir-Blodgett films

    Institute of Scientific and Technical Information of China (English)

    Yi Ming Liu; Sui Ping Deng; Hui Zheng; Jian Ming Ouyang

    2007-01-01

    The ring patterns of calcium oxalate crystals were induced by domains in Langmuir-Blodgett (LB) films of dipalmitoylpho-sphatidylcholine (DPPC). The result was explained by the defects at the ring boundaries of liquid condensed (LC) and liquid expanded (LE) phases of LB film. These boundaries could provide less free energy and much more nucleating sites for COM crystals.

  7. Hydration process of multi-stacked phospholipid bilayers to form giant vesicles

    CERN Document Server

    Hishida, M; Yamada, N L; Yoshikawa, K

    2005-01-01

    A hydration process of multi-stacked phospholipid bilayers to form giant vesicles was investigated by means of time-resolved small angle X-ray scattering. It is found that the hydration of lipids in the liquid-crystalline phase proceeds with two stages: In the early stage until about 150 s after the hydration, lipid bilayers on a solid substrate swell about 20 % and arrive at a quasi-stable state. In the late stage, after several hundreds seconds, lipid bilayers gradually peel off from the stack. On the other hand, in case of a lipid in the gel phase, only the early stage is observed. These behaviors correspond to the ability of the giant vesicle formation depending on the lipid phases. The kinetics of the peeling-off process is discussed in terms of the Kramers' formulas by considering the effect of the unbinding transition.

  8. Supported lipid bilayers as templates to design manganese oxide nanoparticles

    Indian Academy of Sciences (India)

    J Maheshkumar; B Sreedhar; B U Nair; A Dhathathreyan

    2012-09-01

    This work reports on the preparation of nanoclusters of manganese oxide using biotemplating techniques. Supported lipid bilayers (SLBs) on quartz using cationic lipid [Dioctadecyldimethylammonium bromide (DOMA)] and mixed systems with neutral phospholipids dipalmitoyl phosphatidylcholine (DPPC) and dioleoyl phosphatidylcholine (DOPC) have been used as templates to synthesize these nanoparticles in a waterbased medium at room temperature. The Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) show manganese oxide nanostructures that are composed of crystals or small clusters in the size range of 20-50 nm in diameter. Small angle XRD showed that template removal through calcining process results in nanostructures of the manganese oxide in sizes from 30 to 50 nm. Using these organized assemblies it is possible to control the nano and mesoscopic morphologies of particles and both rod-like and spherical particles can be synthesized.

  9. Effects of butanol isomers on dipalmitoylphosphatidylcholine bilayer membranes.

    Science.gov (United States)

    Reeves, Megan D; Schawel, Adam K; Wang, Weidong; Dea, Phoebe

    2007-06-01

    Differential scanning calorimetry and (31)P-NMR were used to study the effects of butanol isomers on the thermotropic phase behavior of dipalmitoylphosphatidylcholine (DPPC) bilayers. The threshold concentration for the onset of interdigitation for each isomer was determined by the disappearance of the pretransition and the onset of a large hysteresis between the heating and cooling scans of the gel-to-liquid main transition. The threshold concentration was found to correlate with increased solubility of the isomers in the aqueous phase, led by tert-butanol. However, as the solution concentration of tert-butanol increased, there was an abrupt shrinking of the hysteresis, initially with well-resolved shoulder peaks indicating mixed phases. The eventual disappearance of the shoulder peaks was correlated with a breakdown of the multilamellar structure identified using (31)P-NMR.

  10. A DSC and FTIR spectroscopic study of the effects of the epimeric coprostan-3-ols and coprostan-3-one on the thermotropic phase behaviour and organization of dipalmitoylphosphatidylcholine bilayer membranes: Comparison with their 5-cholesten analogues.

    Science.gov (United States)

    Benesch, Matthew G K; Lewis, Ruthven N A H; Mannock, David A; McElhaney, Ronald N

    2015-05-01

    We present the results of a comparative differential calorimetric and Fourier transform infrared spectroscopic study of the effect of cholesterol and five analogues on the thermotropic phase behaviour and organization of dipalmitoylphosphatidylcholine bilayer membranes. These sterols/steroids differ in both the nature and stereochemistry of the polar head group at C3 (β-OH, α-OH or CO) and in the presence or absence of a double bond in ring B and in the orientation of rings A and B. The Δ(5) sterols/steroid have a trans rather than a cis ring A/B junction, and the concentration of these compounds required to abolish the DPPC pretransition, inversely related to their relative ability to disorder gel state DPPC bilayers, decreases in the order β-OH > α-OH > CO. However, in the saturated ring junction-inverted (cis) series, these concentrations are much more similar, regardless of polar head group chemical structure. Similarly, the residual enthalpy of the DPPC main phase transition at 50 mol% sterol/steroid, which is inversely related to the miscibility of these compounds in fluid DPPC bilayers, also increases in the order β-OH > α-OH > CO, but this effect is attenuated in the saturated series with an inverted ring A/B orientation. Moreover, replacement of the double bond at C5-C6 with a saturated linkage and inversion of the ring A/B junction reduces both sterol/steroid solubility and the ability to order the hydrocarbon chains of fluid DPPC molecules all cases. Thus, the characteristic effects of sterols/steroids on fluid lipid bilayers are generally optimal when an OH group rather than CO group is present at C3, and when this OH group is in the equatorial (β) orientation, and when the orientation of the ring A/B fusion is trans rather than cis. Overall, these results demonstrate that variations in the saturation and stereochemistry of the steroid ring system influence the effect of variations in the nature and stereochemistry of the polar headgroup at C3

  11. Penetration and growth of DPPC/DHPC bicelles inside the stratum corneum of the skin.

    Science.gov (United States)

    Barbosa-Barros, L; de la Maza, A; Estelrich, J; Linares, A M; Feliz, M; Walther, P; Pons, R; López, O

    2008-06-03

    The effect of dipalmitoyl phosphatidylcholine (DPPC)/dihexanoyl phosphatidylcholine (DHPC) bicelles on the microstructure of pig stratum corneum (SC) in vitro was evaluated. The physicochemical characterization of these nanoaggregates revealed small disks with diameters around 15 nm and a thickness of 5.4 nm. Upon dilution, the bicelles grow and transform into vesicles. Cryogenic scanning electron microscopy (cryo-SEM) images of the SC pieces treated with this system showed vesicles of about 200 nm and lamellar-like structures in the intercellular lipid areas. These vesicles probably resulted from the growth and molecular rearrangement of the DPPC/DHPC bicelles after penetrating the SC. The presence of lamellar-like structures is ascribed to the interaction of the lipids from bicelles with the SC lipids. The bicellar system used is suitable to penetrate the skin SC and to reinforce the intercellular lipid areas, constituting a promising tool for skin applications.

  12. Effects of oxyethylated glycerol cryoprotectants on phase transitions of DPPC model membranes

    Directory of Open Access Journals (Sweden)

    Kasian N. A.

    2015-04-01

    Full Text Available Aim. To determine the effect of the oxyethylated glycerol cryoprotectants (OEGn with polymerization degrees n = 5, 25, 30 on the phase states and phase transitions of dipalmitoylphosphatidylcholine (DPPC-based model membranes. Methods. Differential scanning calorimetry. Results. Model lipid membranes on water/OEGn and water/glycerol subphases with varying cryoprotectant concentrations from 0 to ~ 100 % w/w were studied. A significant raise in the pre-transition and main phase transition temperatures with increasing OEGn concentration was noted whereas the membrane melting peak persist to 100 % w/w OEGn. A sharp increase in the melting enthalpy was observed for OEGn = 5. Conclusions. The solvating ability of the subphase in DPPC membranes decreases in the order water > glycerol > OEGn = 5 > OEGn = 25 > OEGn = 30, which correlates with the relative number of groups effectively contributing to the solvation process.

  13. Critical behaviour in DOPC/DPPC/cholesterol mixtures: static (2)H NMR line shapes near the critical point.

    Science.gov (United States)

    Davis, James H; Schmidt, Miranda L

    2014-05-06

    Static (2)H NMR spectroscopy is used to study the critical behavior of mixtures of 1,2-dioleoyl-phosphatidylcholine/1,2-dipalmitoyl-phosphatidylcholine (DPPC)/cholesterol in molar proportion 37.5:37.5:25 using either chain perdeuterated DPPC-d62 or chain methyl deuterated DPPC-d6. The temperature dependence of the first moment of the (2)H spectrum of the sample made with DPPC-d62 and of the quadrupolar splittings of the chain-methyl-labeled DPPC-d6 sample are directly related to the temperature dependence of the critical order parameter η, which scales as [Formula: see text] near the critical temperature. Analysis of the data reveals that for the chain perdeuterated sample, the value of Tc is 301.51 ± 0.1 K, and that of the critical exponent, βc = 0.391 ± 0.02. The line shape analysis of the methyl labeled (d6) sample gives Tc = 303.74 ± 0.07 K and βc = 0.338 ± 0.009. These values obtained for βc are in good agreement with the predictions of a three-dimensional Ising model. The difference in critical temperature between the two samples having nominally the same molar composition arises because of the lowering of the phase transition temperature that occurs due to the perdeuteration of the DPPC.

  14. Effect of sodium deoxycholate and sodium cholate on DPPC vesicles: A fluorescence anisotropy study with diphenylhexatriene

    Indian Academy of Sciences (India)

    Usharani Subuddhi; Ashok K Mishra

    2007-03-01

    Effects of two bile salts, namely sodium deoxycholate (NaDC) and sodium cholate (NaC), on DPPC small unilamellar vesicles have been investigated using the steady-state fluorescence anisotropy () of diphenylhexatriene (DPH) as a tool. It was found that the variation of is sensitive enough to monitor different stages of interaction of bile salts with DPPC vesicles. NaDC induced significant changes in the membrane well below its CMC (6 mM). Even at 4 mM, which is still lower than the CMC, the phospholipids were completely solubilised by the NaDC micelles. The effect of NaC on DPPC vesicles, however, was much less significant, especially in the sub-micellar concentration regime. Being more hydrophilic NaC does not interact with the membrane efficiently. Complete solubilisation of phospholipids took place only when the concentration of NaC was above its CMC (16 mM). The experiments also showed that the bile salt-induced changes of vesicle structure were strongly dependent on the concentration of the bile salt and not on the molar ratio of lipid and bile salt.

  15. Control of a redox reaction on lipid bilayer surfaces by membrane dipole potential.

    Science.gov (United States)

    Alakoskela, J I; Kinnunen, P K

    2001-01-01

    Nitro-2,1,3-benzoxadiazol-4-yl (NBD) group is a widely used, environment-sensitive fluorescent probe. The negatively charged dithionite rapidly reduces the accessible NBD-labeled lipids in liposomes to their corresponding nonfluorescent derivatives. In this study both the phospholipid headgroup and acyl chain NBD-labeled L-alpha-1,2-dipalmitoyl-sn-glycero-3-phospho-[N-(4-nitrobenz-2-oxa-1,3-diazole)-ethanolamine] (DPPN) and 1-acyl-2-[12-[(7-nitro-2,1,3-benzoxadiazol-4-yl)amino]dodecanoyl]-sn-glycero-3-phosphocholine (NBD-PC), respectively, were employed. The correlation of both the rate coefficient k(1) of the redox reaction and the fluorescence properties of the two probes with the membrane dipole potential Psi in fluid dipalmitoylglycerophosphocholine (DPPC) liposomes is demonstrated. When Psi of the bilayer was varied (decreased by phloretin or increased by 6-ketocholestanol), the value for k1 decreased for both DPPN and NBD-PC with increasing Psi. For both fluorophores a positive correlation to Psi was evident for the relative fluorescence emission intensity (RFI, normalized to the emission of the fluorophore in a DPPC matrix). The relative changes in emission intensity as a function of Psi were approximately equal for both NBD derivatives. Changes similar to those caused by phloretin were seen when dihexadecylglycerophosphocholine (DHPC) was added to DPPC liposomes, in keeping with the lower dipole potential for the former lipid compound compared with DPPC. These effects of Psi on NBD fluorescence should be taken into account when interpreting data acquired using NBD-labeled lipids as fluorescent probes.

  16. Neutron and X-ray Scattering From Single Supported Lipid Bilayers: Reflectometry, Grazing Incidence In-Plane Diffraction and Off-Specular Scattering

    Science.gov (United States)

    Majewski, Jaroslaw

    2010-03-01

    Biological membranes mediate transport and communication between the cell and its surroundings. They defend the cell against invasive agents, and most present day drugs interact with membrane components. Complexity of the cell membranes renders many of their characteristics impenetrable to fundamental physical studies. As a result, a significant emphasis has been placed on developing model lipid membranes that facilitate the physical and chemical characterization of particular membrane features. X-ray (XR) and neutron reflectivity (NR) and grazing incidence X-ray diffraction (GIXD) techniques can be utilized to measure the structure of single, supported lipid bilayers in bulk water. GIXD studies demonstrated that bilayers formed by vesicle fusion have more disorder in the inner leaflet compared to structures prepared using the Langmuir-Blodgett/Schaeffer (LB/S) technique. In both cases, only a modest water cushion was detected between the bilayer and substrate. Diffraction from in-plane ordered domains was observed from bilayers prepared by either technique. In the case of 1,2-Dipalmitoyl-sn-Glycero-3-Phosphocholine (DPPC) bilayers, the ordered domains were coupled across both leaflets, scattering as one entity. Contrastingly, the ordered domains were uncoupled in 1,2-Dipalmitoyl-sn-Glycero-3-Phosphoethanolamine (DPPE) bilayers. NR can be effectively used to study polymer-supported single lipid bilayers in bulk water. Using NR and fluorescence microscopy, we demonstrated that a hydrated, surface-tethered polymer network capable of five-fold change in thickness over a 25-37 C temperature range can be a novel support for single DPPC bilayers in a liquid environment. Moderate temperature change swells the polymer, lifting the membrane from the substrate, creating a nearly aqueous cushion. Additionally, as the polymer swells, it promotes both in- and out-of-plane undulations in the supported membrane. Off-specular neutron scattering was used to deduce the in

  17. The molecular organization of prenylated flavonoid xanthohumol in DPPC multibilayers: X-ray diffraction and FTIR spectroscopic studies.

    Science.gov (United States)

    Arczewska, Marta; Kamiński, Daniel M; Górecka, Ewa; Pociecha, Damian; Rój, Edward; Sławińska-Brych, Adrianna; Gagoś, Mariusz

    2013-02-01

    Xanthohumol (XN) is the major prenylated flavonoid found in hop resin. It has attracted considerable attention in recent years due to its wide spectrum of biological activities and the beneficial effect on human health. Since lipid membrane is first target for biologically active compounds, we decided to investigate the influence of XN on the dipalmitoylphosphatidylcholine (DPPC) multibilayers. Interactions of XN with DPPC were investigated as a function of temperature and its concentration by using X-ray diffraction and the ATR-FTIR spectroscopy techniques. The aim of understanding the mechanisms of molecular interactions between XN and DPPC was to indicate the localization of the XN with respect to the membrane and the type of interaction with phospholipids. The results revealed that XN changes the physical properties of the DPPC multibilayers in the form of dry film. A new complex formation between XN and DPPC is reported. The detailed analysis of refraction effect indicates the changes in electron density ratio between hydrophobic and hydrophilic zones of lipid at phase transition. This is in compliance with reported changes in FTIR spectra where at pretransition XN moves from interface region between polar heads to the neighborhood of phosphate groups.

  18. Lipid asymmetry in DLPC/DSPC supported lipid bilayers, a combined AFM and fluorescence microscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Lin, W; Blanchette, C D; Ratto, T V; Longo, M L

    2005-06-20

    A fundamental attribute of cell membranes is transmembrane asymmetry, specifically the formation of ordered phase domains in one leaflet that are compositionally different from the opposing leaflet of the bilayer. Using model membrane systems, many previous studies have demonstrated the formation of ordered phase domains that display complete transmembrane symmetry but there have been few reports on the more biologically relevant asymmetric membrane structures. Here we report on a combined atomic force microscopy (AFM) and fluorescence microscopy study whereby we observe three different states of transmembrane symmetry in phase-separated supported bilayers formed by vesicle fusion. We find that if the leaflets differ in gel-phase area fraction, then the smaller domains in one leaflet are in registry with the larger domains in the other leaflet and the system is dynamic. In a presumed lipid flip-flop process similar to Ostwald Ripening, the smaller domains in one leaflet erode away while the large domains in the other leaflet grow until complete compositional asymmetry is reached and remains stable. We have quantified this evolution and determined that the lipid flip-flop event happens most frequently at the interface between symmetric and asymmetric DSPC domains. If both leaflets have nearly identical area fraction of gel-phase, gel-phase domains are in registry and are static in comparison to the first state. The stability of these three DSPC domain distributions, the degree of registry observed, and the domain immobility have direct biological significance with regards to maintenance of lipid asymmetry in living cell membranes, communication between inner leaflet and outer leaflet, membrane adhesion, and raft mobility.

  19. Dynamics, Surface Electrostatics and Phase Properties of Nanoscale Curved Lipid Bilayers

    Science.gov (United States)

    Koolivand, Amir

    Surface electrostatic potential of a lipid bilayer governs many vital functions of living cells. Several classes of proteins are known of exhibiting strong binding preferences to curved lipid bilayer surfaces. In this project we employed electron paramagnetic resonance (EPR) of a recently introduced phospholipid (IMTSL-PTE) bearing a pH-sensitive nitroxide covalently attached to the lipid head group to measure the surface electrostatics of the lipid membrane and nanopore-confined lipid bilayers as a function of the bilayer curvature. The pKa of the ionizable group of this lipid-based spin probe is reporting on the bilayer surface electrostatics potential by changes in the EPR spectra. Specifically, both rotational dynamics and magnetic parameters of the nitroxide are affected by the probe protonation. Effect of curvature on the surface electrostatic potential and dynamics of lipid bilayer was studied for POPG and DMPG unilamellar vesicles (ULVs). It was found that the magnitude of the negative surface electrostatic potential increased upon decrease in the vesicle diameter for the bilayers in the fluid phase; however, no significant changes were observed for DMPG ULVs in a gel phase. We speculate that biologically relevant fluid bilayer phase allows for a larger variability in the lipid packing density in the lipid polar head group region than a more ordered gel phase and it is likely that the lipid flip-flop is responsible for pH equilibration of IMTSL-PTE. The kinetic EPR study of nitroxide reduction showed that the rate of flip-flop is in the order of 10-5 s-1. The flip-flop rate constant increases when vesicle size deceases. Oxygen permeability measured by X-ban EPR decreases in higher curved vesicles---an observation that is consistent with a tighter packing in smaller vesicles. Partitioning of a small nitroxide molecule TEMPO into ULVs was measured by X-band (9 GHz) and W-band (95 GHz) EPR spectroscopy. The partitioning coefficient of this probe in the lipid

  20. Hydration lubrication and shear-induced self-healing of lipid bilayer boundary lubricants in phosphatidylcholine dispersions.

    Science.gov (United States)

    Sorkin, Raya; Kampf, Nir; Zhu, Linyi; Klein, Jacob

    2016-03-14

    Measurements of normal and shear (frictional) forces between mica surfaces across small unilamellar vesicle (SUV) dispersions of the phosphatidylcholine (PC) lipids DMPC (14:0), DPPC (16:0) and DSPC (18:0) and POPC (16:0, 18:1), at physiologically high pressures, are reported. We have previously studied the normal and shear forces between two opposing surfaces bearing PC vesicles across pure water and showed that liposome lubrication ability improved with increasing acyl chain length, and correlated strongly with the SUV structural integrity on the substrate surface (DSPC > DPPC > DMPC). In the current study, surprisingly, we discovered that this trend is reversed when the measurements are conducted in SUV dispersions, instead of pure water. In their corresponding SUV dispersion, DMPC SUVs ruptured and formed bilayers, which were able to provide reversible and reproducible lubrication with extremely low friction (μ lubrication, but with slightly higher friction coefficients (μ = 10(-3)-10(-4)). We believe these differences originate from fast self-healing of the softer surface layers (which are in their liquid disordered phase, POPC, or close to it, DMPC), which renders the robustness of the DPPC or DSPC (both in their solid ordered phase) less important in these conditions. Under these circumstances, the enhanced hydration of the less densely packed POPC and DMPC surface layers is now believed to play an important role, and allows enhanced lubrication via the hydration lubrication mechanism. Our findings may have implications for the understanding of complex biological systems such us biolubrication of synovial joints.

  1. Fluorescent molecular probes based on excited state prototropism in lipid bilayer membrane

    Science.gov (United States)

    Mohapatra, Monalisa; Mishra, Ashok K.

    2012-03-01

    Excited state prototropism (ESPT) is observed in molecules having one or more ionizable protons, whose proton transfer efficiency is different in ground and excited states. The interaction of various ESPT molecules like naphthols and intramolecular ESPT (ESIPT) molecules like hydroxyflavones etc. with different microheterogeneous media have been studied in detail and excited state prototropism as a probe concept has been gaining ground. The fluorescence of different prototropic forms of such molecules, on partitioning to an organized medium like lipid bilayer membrane, often show sensitive response to the local environment with respect to the local structure, physical properties and dynamics. Our recent work using 1-naphthol as an ESPT fluorescent molecular probe has shown that the incorporation of monomeric bile salt molecules into lipid bilayer membranes composed from dipalmitoylphosphatidylcholine (DPPC, a lung surfactant) and dimyristoylphosphatidylcholine (DMPC), in solid gel and liquid crystalline phases, induce appreciable wetting of the bilayer up to the hydrocarbon core region, even at very low (fisetin, an ESIPT molecule having antioxidant properties, in lipid bilayer membrane has been sensitively monitored from its intrinsic fluorescence behaviour.

  2. Increased adhesion between neutral lipid bilayers: interbilayer bridges formed by tannic acid.

    Science.gov (United States)

    Simon, S A; Disalvo, E A; Gawrisch, K; Borovyagin, V; Toone, E; Schiffman, S S; Needham, D; McIntosh, T J

    1994-06-01

    Tannic acid (TA) is a naturally occurring polyphenolic compound that aggregates membranes and neutral phosolipid vesicles and precipitates many proteins. This study analyzes TA binding to lipid membranes and the ensuing aggregation. The optical density of dispersions of phosphatidylcholine (PC) vesicles increased upon the addition of TA and electron micrographs showed that TA caused the vesicles to aggregate and form stacks of tightly packed disks. Solution calorimetry showed that TA bound to PC bilayers with a molar binding enthalpy of -8.3 kcal/mol and zeta potential measurements revealed that TA imparted a small negative charge to PC vesicles. Monolayer studies showed that TA bound to PC with a dissociation constant of 1.5 microM and reduced the dipole potential by up to 250 mV. Both the increase in optical density and decrease in dipole potential produced by TA could be reversed by the addition of polyvinylpyrrolidone, a compound that chelates TA by providing H-bond acceptor groups. NMR, micropipette aspiration, and x-ray diffraction experiments showed that TA incorporated into liquid crystalline PC membranes, increasing the area per lipid molecule and decreasing the bilayer thickness by 2 to 4%. 2H-NMR quadrupole splitting measurements also showed that TA associated with a PC molecule for times much less than 10(-4) s. In gel phase bilayers, TA caused the hydrocarbon chains from apposing monolayers to fully interdigitate. X-ray diffraction measurements of both gel and liquid crystalline dispersions showed that TA, at a critical concentration of about 1 mM, reduced the fluid spacing between adjacent bilayers by 8-10 A. These data place severe constraints on how TA can pack between adjacent bilayers and cause vesicles to adhere. We conclude that TA promotes vesicle aggregation by reducing the fluid spacing between bilayers by the formation of transient interbilayer bridges by inserting its digallic acid residues into the interfacial regions of adjacent bilayers

  3. The additional phase transition of DPPC monolayers at high surface pressure confirmed by GIXD study

    DEFF Research Database (Denmark)

    Shen, Chen; Serna, Jorge B. de la; Struth, Bernd

    Pulmonary surfactant forms the alveolar monolayer at the air/aqueous interface within the lung. During the breathing process, the surface pressure periodically varies from ~40mN/m up to ~70mN/m. The film is mechanically stable during this rapid and reversible expansion. The monolayer consists...... of ~90% of lipid with 10% integrated proteins. Among its lipid compounds, di- palmitoyl-phosphatidylcholine (DPPC) dominates (~45wt%). No other lipid but DPPC was so far reported to be compressible to very high surface pressure (~70mN/m) before its monolayer collapsed. Its liquid......-expanded/liquid-condensed (LE/LC) phase transition at ~10mN/m is well known. Here we present results from Langmuir isotherm measurements that evidence a so far not documented second phase transition at elevated surface pressure Π (~50mN/m). The varying lateral structures of the monolayer at 8mN/m, 20mN/m, 30mN/m, 40mN/m, 50m...

  4. Asymmetric distribution of cone-shaped lipids in a highly curved bilayer revealed by a small angle neutron scattering technique

    Energy Technology Data Exchange (ETDEWEB)

    Sakuma, Y; Imai, M [Department of Physics, Ochanomizu University, Bunkyo, Tokyo 112-8610 (Japan); Urakami, N [Department of Physics and Information Sciences, Yamaguchi University, Yamaguchi 753-8512 (Japan); Taniguchi, T, E-mail: imai@phys.ocha.ac.jp [Department of Chemical Engineering, Kyoto University, Kyoto 606-8510 (Japan)

    2011-07-20

    We have investigated the lipid sorting in a binary small unilamellar vesicle (SUV) composed of cone-shaped (1,2-dihexanoyl-sn-glycero-3-phosphocholine: DHPC) and cylinder-shaped (1,2-dipalmitoyl-sn-glycero-3-phosphocholine: DPPC) lipids. In order to reveal the lipid sorting we adopted a contrast matching technique of small angle neutron scattering (SANS), which extracts the distribution of deuterated lipids in the bilayer quantitatively without steric modification of lipids as in fluorescence probe techniques. First the SANS profile of protonated SUVs at a film contrast condition showed that SUVs have a spherical shape with an inner radius of 190 A and a bilayer thickness of 40 A. The SANS profile of deuterated SUVs at a contrast matching condition showed a characteristic scattering profile, indicating an asymmetric distribution of cone-shaped lipids in the bilayer. The characteristic profile was described well by a spherical bilayer model. The fitting revealed that most DHPC molecules are localized in the outer leaflet. Thus the shape of the lipid is strongly coupled with the membrane curvature. We compared the obtained asymmetric distribution of the cone-shaped lipids in the bilayer with the theoretical prediction based on the curvature energy model.

  5. Asymmetric distribution of cone-shaped lipids in a highly curved bilayer revealed by a small angle neutron scattering technique

    Science.gov (United States)

    Sakuma, Y.; Urakami, N.; Taniguchi, T.; Imai, M.

    2011-07-01

    We have investigated the lipid sorting in a binary small unilamellar vesicle (SUV) composed of cone-shaped (1,2-dihexanoyl-sn-glycero-3-phosphocholine: DHPC) and cylinder-shaped (1,2-dipalmitoyl-sn-glycero-3-phosphocholine: DPPC) lipids. In order to reveal the lipid sorting we adopted a contrast matching technique of small angle neutron scattering (SANS), which extracts the distribution of deuterated lipids in the bilayer quantitatively without steric modification of lipids as in fluorescence probe techniques. First the SANS profile of protonated SUVs at a film contrast condition showed that SUVs have a spherical shape with an inner radius of 190 Å and a bilayer thickness of 40 Å. The SANS profile of deuterated SUVs at a contrast matching condition showed a characteristic scattering profile, indicating an asymmetric distribution of cone-shaped lipids in the bilayer. The characteristic profile was described well by a spherical bilayer model. The fitting revealed that most DHPC molecules are localized in the outer leaflet. Thus the shape of the lipid is strongly coupled with the membrane curvature. We compared the obtained asymmetric distribution of the cone-shaped lipids in the bilayer with the theoretical prediction based on the curvature energy model.

  6. Localization and interaction of hydroxyflavones with lipid bilayer model membranes: a study using DSC and multinuclear NMR.

    Science.gov (United States)

    Sinha, Ragini; Joshi, Akshada; Joshi, Urmila J; Srivastava, Sudha; Govil, Girjesh

    2014-06-10

    The localization and interaction of six naturally occurring flavones (FLV, 5HF, 6HF, 7HF, CHY and BLN) in DPPC bilayers were studied using DSC and multi-nuclear NMR. DSC results indicate that FLV and 6HF interact with alkyl chains. The (1)H NMR shows interaction of flavones with the sn-glycero region. Ring current induced chemical shifts indicate that 6HF and BLN acquire parallel orientation in bilayers. 2D NOESY spectra indicate partitioning of the B-ring into the alkyl chain region. The DSC, NMR and binding studies indicate that 5HF and 7HF are located near head group region, while 6HF, CHY and BLN are located in the vicinity of sn-glycero region, and FLV is inserted deepest in the membrane.

  7. Cholesterol Flip-Flop Dynamics in a Phospholipid Bilayer: A 10 Microsecond All-Atom Molecular Dynamics Simulation

    Science.gov (United States)

    Choubey, Amit; Nomura, Ken-Ichi; Kalia, Rajiv; Nakano, Aiichiro; Vashishta, Priya

    2012-02-01

    Cholesterol (CHOL) molecules play a key role in modulating the rigidity of cell membranes, and controlling intracellular transport and signal transduction. Using all-atom molecular dynamics and the parallel replica approach, we study the effect of CHOL molecules on mechanical stresses across a dipalmitoylphosphatidycholine (DPPC)-CHOL bilayer, and the mechanism by which CHOL molecules migrate from one bilayer leaflet to the other (flip-flop events). On average, we observe a CHOL flip-flop event in half-a-microsecond. Once a CHOL flip-flop event is triggered, the inter-leaflet migration occurs in about 62 nanoseconds. The energy barrier associated with flip-flop events is found to be 73 kJ/mol. Results for membrane rigidity as a function of CHOL concentration will also be presented.

  8. A diffuse-interface modeling for liquid solution-solid gel phase transition of physical hydrogel with nonlinear deformation.

    Science.gov (United States)

    Li, Hua; Wu, Tao

    2016-10-01

    A diffuse-interface model is presented in this paper for simulation of the evolution of phase transition between the liquid solution and solid gel states for physical hydrogel with nonlinear deformation. The present domain covers the gel and solution states as well as a diffuse interface between them. They are indicated by the crosslink density in such a way that the solution phase is identified as the state when the crosslink density is small, while the gel as the state if the crosslink density becomes large. In this work, a novel order parameter is thus defined as the crosslink density, which is homogeneous in each distinct phase and smoothly varies over the interface from one phase to another. In this model, the constitutive equations, imposed on the two distinct phases and the interface, are formulated by the second law of thermodynamics, which are in the same form as those derived by a different approach. The present constitutive equations include a novel Ginzburg-Landau type of free energy with a double-well profile, which accounts for the effect of crosslink density. The present governing equations include the equilibrium of forces, the conservations of mass and energy, and an additional kinetic equation imposed for phase transition, in which nonlinear deformation is considered. The equilibrium state is investigated numerically, where two stable phases are observed in the free energy profile. As case studies, a spherically symmetrical solution-gel phase transition is simulated numerically for analysis of the phase transition of physical hydrogel.

  9. Phospholipid barrier to fibrinolysis: role for the anionic polar head charge and the gel phase crystalline structure.

    Science.gov (United States)

    Váradi, Balázs; Kolev, Krasimir; Tenekedjiev, Kiril; Mészáros, Gyöngyi; Kovalszky, Ilona; Longstaff, Colin; Machovich, Raymund

    2004-09-17

    The massive presence of phospholipids is demonstrated in frozen sections of human arterial thrombi. Purified platelet phospholipids and synthetic phospholipids retard in vitro tissue-type plasminogen activator (tPA)-induced fibrinolysis through effects on plasminogen activation and plasmin function. The inhibition of plasminogen activation on the surface of fibrin correlates with the fraction of anionic phospholipid. The phospholipids decrease the amount of tPA penetrating into the clot by 75% and the depth of the reactive surface layer occupied by the activator by up to 30%, whereas for plasmin both of these parameters decrease by approximately 50%. The phospholipids are not only a diffusion barrier, they also bind the components of the fibrinolytic system. Isothermal titration calorimetry shows binding characterized with dissociation constants in the range 0.35-7.64 microm for plasmin and tPA (lower values with more negative phospholipids). The interactions are endothermic and thermodynamically driven by an increase in entropy, probably caused by the rearrangements in the ordered gel structure of the phospholipids (in line with the stronger inhibition at gel phase temperatures compared with liquid crystalline phase temperatures). These findings show a phospholipid barrier, which should be overcome during lysis of arterial thrombi.

  10. SAXS and ATR-FTIR studies on EBT-TSX mixtures in their sol-gel phases.

    Science.gov (United States)

    Hirun, Namon; Rugmai, Supagorn; Sangfai, Tanatchaporn; Tantishaiyakul, Vimon

    2012-11-01

    Our previous study demonstrated that mixtures of tamarind seed xyloglucan (TSX) with appropriate concentrations of eriochrome black T (EBT) produced a gel that could be of benefit for medical use. Here, the sol-gel systems of various fresh and aged mixtures were further investigated using rheological measurements. The nanostructural changes of EBT-TSX sol-gel phases were analyzed using SAXS. The interactions between EBT and TSX in the sol and gel states were examined using ATR-FTIR. SAXS data analysis demonstrated that the mixture containing lower concentration of EBT formed rod-like structures and that with higher concentrations of EBT produced flat particles. The sizes of the TSX structures from the aged mixtures in the gel stage were larger than those from the same mixtures in the sol state. ATR-FTIR spectral changes revealed that the azo and sulfonic acid groups of EBT interacted with the TSX, and the characteristic spectrum of the sulfonic acid group of EBT could discriminate between the sol and gel state of the EBT-TSX systems. The interactions between EBT and TSX may cause conformational changes to TSX and facilitate the sol-gel transition or formation of a gel.

  11. Compositional and structural characterization of monolayers and bilayers composed of native pulmonary surfactant from wild type mice.

    Science.gov (United States)

    Bernardino de la Serna, Jorge; Hansen, Soren; Berzina, Zane; Simonsen, Adam C; Hannibal-Bach, Hans K; Knudsen, Jens; Ejsing, Christer S; Bagatolli, Luis A

    2013-11-01

    This work comprises a structural and dynamical study of monolayers and bilayers composed of native pulmonary surfactant from mice. Spatially resolved information was obtained using fluorescence (confocal, wide field and two photon excitation) and atomic force microscopy methods. Lipid mass spectrometry experiments were also performed in order to obtain relevant information on the lipid composition of this material. Bilayers composed of mice pulmonary surfactant showed coexistence of distinct domains at room temperature, with morphologies and lateral packing resembling the coexistence of liquid ordered (lo)/liquid disordered (ld)-like phases reported previously in porcine lung surfactant. Interestingly, the molar ratio of saturated (mostly DPPC)/non-saturated phospholipid species and cholesterol measured in the innate material corresponds with that of a DOPC/DPPC/cholesterol mixture showing lo/ld phase coexistence at a similar temperature. This suggests that at quasi-equilibrium conditions, key lipid classes in this complex biological material are still able to produce the same scaffold observed in relevant but simpler model lipid mixtures. Also, robust structural and dynamical similarities between mono- and bi-layers composed of mice pulmonary surfactant were observed when the monolayers reach a surface pressure of 30mN/m. This value is in line with theoretically predicted and recently measured surface pressures, where the monolayer-bilayer equivalence occurs in samples composed of single phospholipids. Finally, squeezed out material attached to pulmonary surfactant monolayers was observed at surface pressures near the beginning of the monolayer reversible exclusion plateau (~40mN/m). Under these conditions this material adopts elongated tubular shapes and displays ordered lateral packing as indicated by spatially resolved LAURDAN GP measurements.

  12. Miscibility of dl-α-tocopherol β-glucoside in DPPC monolayer at air/water and air/solid interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Neunert, G. [Department of Physics and Biophysics, Poznan University of Life Sciences, 60-637 Poznan (Poland); Makowiecki, J.; Piosik, E.; Hertmanowski, R. [Faculty of Technical Physics, Poznan University of Technology, 60-965 Poznan (Poland); Polewski, K. [Department of Physics and Biophysics, Poznan University of Life Sciences, 60-637 Poznan (Poland); Martynski, T., E-mail: tomasz.martynski@put.poznan.pl [Faculty of Technical Physics, Poznan University of Technology, 60-965 Poznan (Poland)

    2016-10-01

    The role of newly synthesized tocopherol glycosidic derivative in modifying molecular organization and phase transitions of phospholipid monolayer at the air/water interface has been investigated. Two-component Langmuir films of dl-α-tocopheryl β-D-glucopyranoside (BG) mixed with dipalmitoyl phosphatidylcholine (DPPC) in the whole range of mole fractions were formed at the water surface. An analysis of surface pressure versus mean molecular area (π-A) isotherms and Brewster angle microscope images showed that the presence of BG molecules changes the structure and packing of the DPPC monolayer in a BG concentration dependent manner. BG molecules incorporated into DPPC monolayer inhibit its liquid expanded to liquid condensed phase transition proportionally to the BG concentration. The monolayers were also transferred onto solid substrates and visualized using an atomic force microscope. The results obtained indicate almost complete miscibility of BG and DPPC in the monolayers at surface pressures present in the biological cell membrane (30-35·10{sup -3} N·m{sup -1}) for a BG mole fraction as high as 0.3. This makes the monolayer less packed and more disordered, leading to an increased permeability. The results support our previous molecular dynamics simulation data. - Highlights: • Langmuir films of α-tocopherol derivative with DPPC was studied thermodynamically. • Mixed DPPC/BG films were transferred onto mica substrates for topography imaging by using AFM. • Miscibility of BG/DPPC films at surface pressures present in membranes was observed up to MF = 0.3.

  13. Development of lamellar gel phase emulsion containing marigold oil (Calendula officinalis) as a potential modern wound dressing.

    Science.gov (United States)

    Okuma, C H; Andrade, T A M; Caetano, G F; Finci, L I; Maciel, N R; Topan, J F; Cefali, L C; Polizello, A C M; Carlo, T; Rogerio, A P; Spadaro, A C C; Isaac, V L B; Frade, M A C; Rocha-Filho, P A

    2015-04-25

    Appropriate therapeutics for wound treatments can be achieved by studying the pathophysiology of tissue repair. Here we develop formulations of lamellar gel phase (LGP) emulsions containing marigold (Calendula officinalis) oil, evaluating their stability and activity on experimental wound healing in rats. LGP emulsions were developed and evaluated based on a phase ternary diagram to select the best LGP emulsion, having a good amount of anisotropic structure and stability. The selected LGP formulation was analyzed according to the intrinsic and accelerated physical stability at different temperatures. In addition, in vitro and in vivo studies were carried out on wound healing rats as a model. The LGP emulsion (15.0% marigold oil; 10.0% of blend surfactants and 75.0% of purified water [w/w/w]) demonstrated good stability and high viscosity, suggesting longer contact of the formulation with the wound. No cytotoxic activity (50-1000 μg/mL) was observed in marigold oil. In the wound healing rat model, the LGP (15 mg/mL) showed an increase in the leukocyte recruitment to the wound at least on days 2 and 7, but reduced leukocyte recruitment after 14 and 21 days, as compared to the control. Additionally, collagen production was reduced in the LGP emulsion on days 2 and 7 and further accelerated the process of re-epithelialization of the wound itself. The methodology utilized in the present study has produced a potentially useful formulation for a stable LGP emulsion-containing marigold, which was able to improve the wound healing process.

  14. Neutron reflectivity study of substrate surface chemistry effects on supported phospholipid bilayer formation on (1120) sapphire.

    Energy Technology Data Exchange (ETDEWEB)

    Oleson, Timothy A. [University of Wisconsin, Madison; Sahai, Nita [University of Akron; Wesolowski, David J [ORNL; Dura, Joseph A [ORNL; Majkrzak, Charles F [ORNL; Giuffre, Anthony J. [University of Wisconsin, Madison

    2012-01-01

    Oxide-supported phospholipid bilayers (SPBs) used as biomimetric membranes are significant for a broad range of applications including improvement of biomedical devices and biosensors, and in understanding biomineralization processes and the possible role of mineral surfaces in the evolution of pre-biotic membranes. Continuous-coverage and/or stacjed SPBs retain properties (e.,g. fluidity) more similar to native biological membranes, which is desirable for most applications. Using neutron reflectivity, we examined face coverage and potential stacking of dipalmitoylphosphatidylcholine (DPPC) bilayers on the (1120) face of sapphire (a-Al2O3). Nearly full bilayers were formed at low to neutral pH, when the sapphire surface is positively charged, and at low ionic strength (l=15 mM NaCl). Coverage decreased at higher pH, close to the isoelectric point of sapphire, and also at high I>210mM, or with addition of 2mM Ca2+. The latter two effects are additive, suggesting that Ca2+ mitigates the effect of higher I. These trends agree with previous results for phospholipid adsorption on a-Al2O3 particles determined by adsorption isotherms and on single-crystal (1010) sapphire by atomic force microscopy, suggesting consistency of oxide surface chemistry-dependent effects across experimental techniques.

  15. Acceleration of Lateral Equilibration in Mixed Lipid Bilayers Using Replica Exchange with Solute Tempering.

    Science.gov (United States)

    Huang, Kun; García, Angel E

    2014-10-14

    The lateral heterogeneity of cellular membranes plays an important role in many biological functions such as signaling and regulating membrane proteins. This heterogeneity can result from preferential interactions between membrane components or interactions with membrane proteins. One major difficulty in molecular dynamics simulations aimed at studying the membrane heterogeneity is that lipids diffuse slowly and collectively in bilayers, and therefore, it is difficult to reach equilibrium in lateral organization in bilayer mixtures. Here, we propose the use of the replica exchange with solute tempering (REST) approach to accelerate lateral relaxation in heterogeneous bilayers. REST is based on the replica exchange method but tempers only the solute, leaving the temperature of the solvent fixed. Since the number of replicas in REST scales approximately only with the degrees of freedom in the solute, REST enables us to enhance the configuration sampling of lipid bilayers with fewer replicas, in comparison with the temperature replica exchange molecular dynamics simulation (T-REMD) where the number of replicas scales with the degrees of freedom of the entire system. We apply the REST method to a cholesterol and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) bilayer mixture and find that the lateral distribution functions of all molecular pair types converge much faster than in the standard MD simulation. The relative diffusion rate between molecules in REST is, on average, an order of magnitude faster than in the standard MD simulation. Although REST was initially proposed to study protein folding and its efficiency in protein folding is still under debate, we find a unique application of REST to accelerate lateral equilibration in mixed lipid membranes and suggest a promising way to probe membrane lateral heterogeneity through molecular dynamics simulation.

  16. General model of phospholipid bilayers in fluid phase within the single chain mean field theory

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yachong; Baulin, Vladimir A. [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Av. dels Paisos Catalans 26, 43007 Tarragona (Spain); Pogodin, Sergey [Institute of Chemical Research of Catalonia, ICIQ, Av. Paisos Catalans 16, 43007 Tarragona (Spain)

    2014-05-07

    Coarse-grained model for saturated phospholipids: 1,2-didecanoyl-sn-glycero-3-phosphocholine (DCPC), 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC), 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and unsaturated phospholipids: 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), 1,2- dioleoyl-sn-glycero-3-phosphocholine (DOPC) is introduced within the single chain mean field theory. A single set of parameters adjusted for DMPC bilayers gives an adequate description of equilibrium and mechanical properties of a range of saturated lipid molecules that differ only in length of their hydrophobic tails and unsaturated (POPC, DOPC) phospholipids which have double bonds in the tails. A double bond is modeled with a fixed angle of 120°, while the rest of the parameters are kept the same as saturated lipids. The thickness of the bilayer and its hydrophobic core, the compressibility, and the equilibrium area per lipid correspond to experimentally measured values for each lipid, changing linearly with the length of the tail. The model for unsaturated phospholipids also fetches main thermodynamical properties of the bilayers. This model is used for an accurate estimation of the free energies of the compressed or stretched bilayers in stacks or multilayers and gives reasonable estimates for free energies. The proposed model may further be used for studies of mixtures of lipids, small molecule inclusions, interactions of bilayers with embedded proteins.

  17. Improved prediction of bilayer and monolayer properties using a refined BMW-MARTINI force field.

    Science.gov (United States)

    Miguel, Virginia; Perillo, Maria A; Villarreal, Marcos A

    2016-11-01

    Coarse-grained (CG) models allow enlarging the size and time scales that are reachable by atomistic molecular dynamics simulations. A CG force field (FF) for lipids and amino acids that possesses a polarizable water model has been developed following the MARTINI parametrization strategy, the BMW-MARTINI [1]. We tested the BMW-MARTINI FF capability to describe some structural and thermodynamical properties of lipid monolayers and bilayers. We found that, since the surface tension values of oil/water interfaces calculated with the model are not correct, compression isotherms of lipid monolayers present artifacts. Also, this FF predicts DPPC and DAPC bilayers to remain in the Lα phase at temperatures as low as 283K, contrary to the expected from their experimental Tm values. Finally, simulations at constant temperature of bilayers of saturated lipids belonging to PC homologous, showed an increase in the mean molecular area (Mma) upon increasing the chain length, inversely to the experimental observation. We refined BMW-MARTINI FF by modifying as few parameters as possible in order to bring simulated and experimental measurements closer. We have also modified structural parameters of the lipid geometry that do not have direct influence in global properties of the bilayer membranes or monolayers, but serve to approach the obtained CG geometry to atomistic reference values. The refined FF is able to better reproduce phase transition temperatures and Mma for saturated PC bilayers than BMW-MARTINI and MARTINI FF. Finally, the simulated surface pressure-Mma isotherms of PC monolayers resemble the experimental ones and eliminate serious artifacts of previous models.

  18. Tetra- and Penta-Cyclic Triterpenes Interaction with Lipid Bilayer Membrane: A Structural Comparative Study.

    Science.gov (United States)

    Abboud, Rola; Charcosset, Catherine; Greige-Gerges, Hélène

    2016-06-01

    The effect of tetracyclic (cortisol, prednisolone, and 9-fluorocortisol acetate) and pentacyclic (uvaol and erythrodiol) triterpenes (TTPs) on the fluidity of dipalmitoyl phosphatidyl choline (DPPC) liposome membrane was investigated by differential scanning calorimetry, Raman spectroscopy, and fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH). Liposomes were prepared in the absence and presence of TTPs at molar ratios DPPC:TTP 100:1, 100:2.5, and 100:10. All the studied TTPs abolished the pre-transition and modified the intensity of the Raman peak at 715 cm(-1) proving the interaction of TTP molecules with the choline head group of phospholipids. An increase in the Raman height intensity ratios of the peaks I 2935/2880, I 2844/2880, and I 1090/1130, giving information about the ratio disorder/order of the alkyl chains, and a decrease of the main transition temperature demonstrated the interaction of TTPs with the alkyl chains. The tetracyclic TTPs produced broadening of the phase transition profile. Besides, a scarcely splitting of the main transition peak was obtained with prednisolone and 9-fluorocortisol acetate. The results of fluorescence depolarization of DPH showed that the studied molecules fluidized the liposomal membrane at 25, 41, and 50 °C. Pentacyclic TTPs, being more hydrophobic than tetracyclic ones, demonstrated higher fluidizing effect than tetracyclic TTPs in the liquid crystalline phase suggesting a deeper incorporation in the lipid bilayer. The presence of a free polar head group at the ring D seems to control the TTP incorporation in the bilayer and consequently its effect on the membrane fluidity.

  19. The influence of amphotericin B on the molecular organization and structural properties of DPPC lipid membranes modified by sterols

    Science.gov (United States)

    Kamiński, Daniel M.; Pociecha, Damian; Górecka, Ewa; Gagoś, Mariusz

    2015-02-01

    In this work, we studied the influence of the polyene antibiotic amphotericin B (AmB) on dipalmitoylphosphatidylcholine (DPPC) multibilayers modified by cholesterol and ergosterol investigated by means of X-ray diffraction. The periodic structures related to AmB-DPPC-sterol complexes in multibilayers are completely created in temperatures above the main lipid phase transition. The differences between all observed multilayer structures are related to the thickness. Multibilayers composed of lipid and sterols have similar thickness of 51 Å. Addition of amphotericin B leads to creation of new periodic structures. Multibilayers composed of lipid-ergosterol-AmB have thickness of 44 Å which does not change with temperature. Multibilayers composed of lipid-cholesterol-AmB at 20 °C are 43 Å and gets thicker at 50 °C. Most probably this is caused by weaker van der Vaals cholesterol-amphotericin B interactions.

  20. Water replacement hypothesis in atomic detail--factors determining the structure of dehydrated bilayer stacks.

    Science.gov (United States)

    Golovina, Elena A; Golovin, Andrey V; Hoekstra, Folkert A; Faller, Roland

    2009-07-22

    According to the water replacement hypothesis, trehalose stabilizes dry membranes by preventing the decrease of spacing between membrane lipids under dehydration. In this study, we use molecular-dynamics simulations to investigate the influence of trehalose on the area per lipid (APL) and related structural properties of dehydrated bilayers in atomic detail. The starting conformation of a palmitoyloleolylphosphatidylcholine lipid bilayer in excess water was been obtained by self-assembly. A series of molecular-dynamics simulations of palmitoyloleolylphosphatidylcholine with different degrees of dehydration (28.5, 11.7, and 5.4 waters per lipid) and different molar trehalose/lipid ratios (1:1) were carried out in the NPT ensemble. Water removal causes the formation of multilamellar "stacks" through periodic boundary conditions. The headgroups reorient from pointing outward to inward with dehydration. This causes changes in the electrostatic interactions between interfaces, resulting in interface interpenetration. Interpenetration creates self-spacing of the bilayers and prevents gel-phase formation. At lower concentrations, trehalose does not separate the interfaces, and acting together with self-spacing, it causes a considerable increase of APL. APL decreases at higher trehalose concentrations when the layer of sugar physically separates the interfaces. When interfaces are separated, the model confirms the water replacement hypothesis.

  1. Water Replacement Hypothesis in Atomic Detail—Factors Determining the Structure of Dehydrated Bilayer Stacks

    Science.gov (United States)

    Golovina, Elena A.; Golovin, Andrey V.; Hoekstra, Folkert A.; Faller, Roland

    2009-01-01

    Abstract According to the water replacement hypothesis, trehalose stabilizes dry membranes by preventing the decrease of spacing between membrane lipids under dehydration. In this study, we use molecular-dynamics simulations to investigate the influence of trehalose on the area per lipid (APL) and related structural properties of dehydrated bilayers in atomic detail. The starting conformation of a palmitoyloleolylphosphatidylcholine lipid bilayer in excess water was been obtained by self-assembly. A series of molecular-dynamics simulations of palmitoyloleolylphosphatidylcholine with different degrees of dehydration (28.5, 11.7, and 5.4 waters per lipid) and different molar trehalose/lipid ratios (1:1) were carried out in the NPT ensemble. Water removal causes the formation of multilamellar “stacks” through periodic boundary conditions. The headgroups reorient from pointing outward to inward with dehydration. This causes changes in the electrostatic interactions between interfaces, resulting in interface interpenetration. Interpenetration creates self-spacing of the bilayers and prevents gel-phase formation. At lower concentrations, trehalose does not separate the interfaces, and acting together with self-spacing, it causes a considerable increase of APL. APL decreases at higher trehalose concentrations when the layer of sugar physically separates the interfaces. When interfaces are separated, the model confirms the water replacement hypothesis. PMID:19619463

  2. The impact of cell-penetrating peptides on membrane bilayer structure during binding and insertion.

    Science.gov (United States)

    Hirst, Daniel J; Lee, Tzong-Hsien; Kulkarni, Ketav; Wilce, Jacqueline A; Aguilar, Marie-Isabel

    2016-08-01

    We have studied the effect of penetratin and a truncated analogue on the bilayer structure using dual polarisation interferometry, to simultaneously measure changes in mass per unit area and birefringence (an optical parameter representing bilayer order) with high sensitivity during the binding and dissociation from the membrane. Specifically, we studied penetratin (RQIKIWFQNRRMKWKK), along with a shortened and biotinylated version known as R8K-biotin (RRMKWKKK(Biotin)-NH2). Overall both peptides bound only weakly to the neutral DMPC and POPC bilayers, while much higher binding was observed for the anionic DMPC/DMPG and POPC/POPG. The binding of penetratin to gel-phase DMPC/DMPG was adequately represented by a two-state model, whereas on the fluid-phase POPC/POPG it exhibited a distinctly different binding pattern, best represented by a three-state kinetic model. However, R8K-biotin did not bind well to DMPC/DMPG and showed a more transitory and superficial binding to POPC/POPG. Comparing the modelling results for both peptides binding to POPC/POPG suggests an important role for a securely bound intermediate prior to penetratin insertion and translocation. Overall these results further elucidate the mechanism of penetratin, and provide another example of the significance of the ability of DPI to measure structural changes and the use of kinetic analysis to investigate the stages of peptide-membrane interactions.

  3. Synthesis and Crystal Structure of [CpRu(η5-C5H5)(dppc)Cl][PF6

    Institute of Scientific and Technical Information of China (English)

    WU Xiang-Hua; YU Guang-Ao; MENG Xiang-Gao; CHEN Yan; REN Yong; LIU Sheng-Hua

    2006-01-01

    The title complex [Ru(η5-C5H5)(dppc)Cl][PF6] has been synthesized by the reaction of [Ru(η5-C5H5)(PPh3)2Cl] with [dppc][PF6] (1,1'-bis(diphenylphosphino)cobaltocenium hexaflurophospate) in CH2Cl2, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 15.754(8), b =13.704(7), c=19.120(10) (A),β=106.148(9)°, V=3965(4) (A)3, Z=4, C40H35Cl3CoF6P3Ru, Mr=988.94, Dc=1.657 g/cm3, F(000) = 1984 and μ(MoKα) = 1.181 mm-1. The final R = 0.0425 and wR = 0.1001 for 7002 independent reflections. The title complex shows a mononuclear Ru(Ⅱ)capped by an η5-Cp ring, a chelating η2-dppc and a terminal chloride to assume a three-legged piano-stool configuration.

  4. Two-component Langmuir monolayers and LB films of DPPC with partially fluorinated alcohol (F8H9OH).

    Science.gov (United States)

    Nakahara, Hiromichi; Hirano, Chikayo; Shibata, Osamu

    2013-01-01

    The interaction of (perfluorooctyl)nonanol (F8H9OH) with dipalmitoylphosphatidylcholine (DPPC) was systematically studied in two-component monolayers at air-water interface. The thermodynamic property and phase morphology of the monolayers were investigated by isotherm measurements and several microscopic methods such as Brewster angle microscopy, fluorescence microscopy, and atomic force microscopy (AFM). The AFM topographies for Langmuir-Blodgett films of F8H9OH exhibit the formation of monodispersed surface micelles. In the two-component system, the incorporation of F8H9OH induces condensation (or solidification) of DPPC monolayers. The excess Gibbs free energy and interaction parameter (or energy) of the two components were calculated from the isotherm data. Both the phase transition pressure for the coexistence of ordered and disordered phases and collapse pressure of monolayers vary with the mole fraction of F8H9OH, indicating binary miscibility between F8H9OH and DPPC within a monolayer state. The miscibility is also confirmed visually by in situ and ex situ microscopy at micro- and nanometer scales.

  5. Calorimetric study on pH-responsive block copolymer grafted lipid bilayers: rational design and development of liposomes.

    Science.gov (United States)

    Pippa, Natassa; Chountoulesi, Maria; Kyrili, Aimilia; Meristoudi, Anastasia; Pispas, Stergios; Demetzos, Costas

    2016-09-01

    This study is focused on chimeric advanced drug delivery nanosystems and specifically on pH-sensitive liposomes, combining lipids and pH-responsive amphiphilic block copolymers. Chimeric liposomes composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and two different forms of block copolymers, i.e. poly(n-butylacrylate)-b-poly(acrylic acid) (PnBA-b-PAA) at 70 and 85% content of PAA at six different molar ratios, each form respectively. PAA block exhibits pH-responsiveness, because of the regulative group of -COOH. -COOH is protonated under acidic pH (pKa ca. 4.2), while remains ionized under basic or neutral pH, leading to liposomes repulse and eventually stability. Lipid bilayers were prepared composed of DPPC and PnBA-b-PAA. Experiments were carried out using differential scanning calorimetry (DSC) in order to investigate their thermotropic properties. DSC indicated disappearance of pre-transition at all chimeric lipid bilayers and slight thermotropic changes of the main transition temperature. Chimeric liposomes have been prepared and their physicochemical characteristics have been explored by measuring the size, size distribution and ζ-potential, owned to the presence of pH-responsive polymer. At percentages containing medium to high amounts of the polymer, chimeric liposomes were found to retain their size during the stability studies. These results were well correlated with those indicated in the DSC measurements of lipid bilayers incorporating polymers in order to explain their physicochemical behavior. The incorporation of the appropriate amount of these novel pH-responsive block copolymers affects thus the cooperativity, the liposomal stabilization and imparts pH-responsiveness.

  6. Nanoparticle-lipid bilayer interactions studied with lipid bilayer arrays

    Science.gov (United States)

    Lu, Bin; Smith, Tyler; Schmidt, Jacob J.

    2015-04-01

    The widespread environmental presence and commercial use of nanoparticles have raised significant health concerns as a result of many in vitro and in vivo assays indicating toxicity of a wide range of nanoparticle species. Many of these assays have identified the ability of nanoparticles to damage cell membranes. These interactions can be studied in detail using artificial lipid bilayers, which can provide insight into the nature of the particle-membrane interaction through variation of membrane and solution properties not possible with cell-based assays. However, the scope of these studies can be limited because of the low throughput characteristic of lipid bilayer platforms. We have recently described an easy to use, parallel lipid bilayer platform which we have used to electrically investigate the activity of 60 nm diameter amine and carboxyl modified polystyrene nanoparticles (NH2-NP and COOH-NP) with over 1000 lipid bilayers while varying lipid composition, bilayer charge, ionic strength, pH, voltage, serum, particle concentration, and particle charge. Our results confirm recent studies finding activity of NH2-NP but not COOH-NP. Detailed analysis shows that NH2-NP formed pores 0.3-2.3 nm in radius, dependent on bilayer and solution composition. These interactions appear to be electrostatic, as they are regulated by NH2-NP surface charge, solution ionic strength, and bilayer charge. The ability to rapidly measure a large number of nanoparticle and membrane parameters indicates strong potential of this bilayer array platform for additional nanoparticle bilayer studies.The widespread environmental presence and commercial use of nanoparticles have raised significant health concerns as a result of many in vitro and in vivo assays indicating toxicity of a wide range of nanoparticle species. Many of these assays have identified the ability of nanoparticles to damage cell membranes. These interactions can be studied in detail using artificial lipid bilayers, which

  7. Interaction of Phenylalanine with DPPC Model Membranes: More Than a Hydrophobic Interaction.

    Science.gov (United States)

    Rosa, A S; Cutro, A C; Frías, M A; Disalvo, E A

    2015-12-31

    The negative free energy previously reported is explained by the stabilization of a PC-Phe (phosphocholine-phenylalanine) complex in the presence of water shown by the decrease in the symmetric stretching frequency of the phosphate group of the lipid (PO2(-)). An entropic contribution due to the disruption of the water network around the phenyl and in the membrane defect may be invoked. The dipole potential decrease is explained by the orientation of the carboxylate opposing to the CO of the lipids with oxygen moiety toward the low hydrated hydrocarbon core. The symmetric bending frequency of NH3(+) group of Phe, decreases in 5.2 cm(-1) in relation to water congruent with zeta potential shift to positive values. The Phe to DPPC dissociation constant is Kd = 2.23 ± 0.09 mM, from which the free energy change is about -4.54 kcal/mol at 25 °C. This may be due to hydrophobic contributions and two hydrogen bonds.

  8. Effect of Melatonin and Cholesterol on the Structure of DOPC and DPPC Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Drolle, E [University of Waterloo, Canada; Kucerka, Norbert [Canadian Neutron Beam Centre and Comelius University (Slovakia); Hoopes, M I [University of Waterloo, Canada; Choi, Y [University of Waterloo, Canada; Katsaras, John [ORNL; Karttunen, M [University of Waterloo, Canada; Leonenko, Z [University of Waterloo, Canada

    2013-01-01

    The cell membrane plays an important role in the molecular mechanism of amyloid toxicity associated with Alzheimer's disease. The membrane's chemical composition and the incorporation of small molecules, such as melatonin and cholesterol, can alter its structure and physical properties, thereby affecting its interaction with amyloid peptides. Both melatonin and cholesterol have been recently linked to amyloid toxicity. Melatonin has been shown to have a protective role against amyloid toxicity. However, the underlying molecular mechanism of this protection is still not well understood, and cholesterol's role remains controversial. We used small-angle neutron diffraction (SAND) from oriented lipid multi-layers, small-angle neutron scattering (SANS) from unilamellar vesicles experiments andMolecular Dynamics (MD) simulations to elucidate non-specific interactions of melatonin and cholesterol with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1,2-dipalmitoyl-snglycero-3-phosphocholine (DPPC) model membranes. We conclude that melatonin decreases the thickness of both model membranes by disordering the lipid hydrocarbon chains, thus increasing membrane fluidity. This result is in stark contrast to the much accepted ordering effect induced by cholesterol, which causes membranes to thicken.

  9. Molecular Dynamics of Lipid Bilayers

    Science.gov (United States)

    1989-08-09

    The aim of this work is to study, by molecular dynamics simulations, the properties of lipid bilayers. We have applied the vectorizable, order-N...fast angle-dependent force/potential algorithms to treat angle bending and torsion. Keywords: Molecular dynamics , Lipid bilayers.

  10. Optical stretching as a tool to investigate the mechanical properties of lipid bilayers.

    Science.gov (United States)

    Solmaz, Mehmet E; Sankhagowit, Shalene; Biswas, Roshni; Mejia, Camilo A; Povinelli, Michelle L; Malmstadt, Noah

    2013-10-07

    Measurements of lipid bilayer bending modulus by various techniques produce widely divergent results. We attempt to resolve some of this ambiguity by measuring bending modulus in a system that can rapidly process large numbers of samples, yielding population statistics. This system is based on optical stretching of giant unilamellar vesicles (GUVs) in a microfluidic dual-beam optical trap (DBOT). The microfluidic DBOT system is used here to measure three populations of GUVs with distinct lipid compositions. We find that gel-phase membranes are significantly stiffer than liquid-phase membranes, consistent with previous reports. We also find that the addition of cholesterol does not alter the bending modulus of membranes composed of a monounsaturated phospholipid.

  11. A study of the antibacterial activity of L-phenylalanine and L-tyrosine esters in relation to their CMCs and their interactions with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC as model membrane.

    Science.gov (United States)

    Joondan, Nausheen; Jhaumeer-Laulloo, Sabina; Caumul, Prakashanand

    2014-01-01

    Cationic amino acid-based surfactants are known to interact with the lipid bilayer of cell membranes resulting in depolarization, lysis and cell death through a disruption of the membrane topology. A range of cationic surfactant analogues derived from L-Phenylalanine (C1-C20) and L-Tyrosine (C8-C14) esters have been synthesized and screened for their antibacterial activity. The esters were more active against gram positive than gram negative bacteria. The activity increased with increasing chain length, exhibiting a cut-off effect at C12 for gram positive and C8/C10 for gram negative bacteria. The cut-off effect for gram negative bacteria was observed at a lower alkyl chain length. The CMC was correlated with the MIC, inferring that micellar activity contribute to the cut-off effect in antibacterial activity. The interaction of the cationic surfactants with the phospholipid vesicles (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC) in the presence of 1-anilino-8-naphthalene sulfonate (ANS) and 1,6-diphenyl-1,3,5-hexatriene (DPH) as fluorescence probes showed that an increase in ionic interaction causes an increase in antibacterial activity. Increase in hydrophobic interaction increases the antibacterial activity only to a certain chain length, attributing to the cut-off effect. Therefore, both electrostatic and hydrophobic interactions, involving the polar and nonpolar moieties are of paramount importance for the bactericidal properties.

  12. Bursting Bubbles and Bilayers

    Directory of Open Access Journals (Sweden)

    Steven P. Wrenn, Stephen M. Dicker, Eleanor F. Small, Nily R. Dan, Michał Mleczko, Georg Schmitz, Peter A. Lewin

    2012-01-01

    Full Text Available This paper discusses various interactions between ultrasound, phospholipid monolayer-coated gas bubbles, phospholipid bilayer vesicles, and cells. The paper begins with a review of microbubble physics models, developed to describe microbubble dynamic behavior in the presence of ultrasound, and follows this with a discussion of how such models can be used to predict inertial cavitation profiles. Predicted sensitivities of inertial cavitation to changes in the values of membrane properties, including surface tension, surface dilatational viscosity, and area expansion modulus, indicate that area expansion modulus exerts the greatest relative influence on inertial cavitation. Accordingly, the theoretical dependence of area expansion modulus on chemical composition - in particular, poly (ethylene glyclol (PEG - is reviewed, and predictions of inertial cavitation for different PEG molecular weights and compositions are compared with experiment. Noteworthy is the predicted dependence, or lack thereof, of inertial cavitation on PEG molecular weight and mole fraction. Specifically, inertial cavitation is predicted to be independent of PEG molecular weight and mole fraction in the so-called mushroom regime. In the “brush” regime, however, inertial cavitation is predicted to increase with PEG mole fraction but to decrease (to the inverse 3/5 power with PEG molecular weight. While excellent agreement between experiment and theory can be achieved, it is shown that the calculated inertial cavitation profiles depend strongly on the criterion used to predict inertial cavitation. This is followed by a discussion of nesting microbubbles inside the aqueous core of microcapsules and how this significantly increases the inertial cavitation threshold. Nesting thus offers a means for avoiding unwanted inertial cavitation and cell death during imaging and other applications such as sonoporation. A review of putative sonoporation mechanisms is then presented

  13. Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

    OpenAIRE

    Schrader, Alex M.; Cheng, Chi-Yuan; Israelachvili, Jacob N.; Han, Songi

    2016-01-01

    Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhause...

  14. Surface electrostatics of lipid bilayers by EPR of a pH-sensitive spin-labeled lipid.

    Science.gov (United States)

    Voinov, Maxim A; Rivera-Rivera, Izarys; Smirnov, Alex I

    2013-01-08

    Many biophysical processes such as insertion of proteins into membranes and membrane fusion are governed by bilayer electrostatic potential. At the time of this writing, the arsenal of biophysical methods for such measurements is limited to a few techniques. Here we describe a, to our knowledge, new spin-probe electron paramagnetic resonance (EPR) approach for assessing the electrostatic surface potential of lipid bilayers that is based on a recently synthesized EPR probe (IMTSL-PTE) containing a reversibly ionizable nitroxide tag attached to the lipids' polar headgroup. EPR spectra of the probe directly report on its ionization state and, therefore, on electrostatic potential through changes in nitroxide magnetic parameters and the degree of rotational averaging. Further, the lipid nature of the probe provides its full integration into lipid bilayers. Tethering the nitroxide moiety directly to the lipid polar headgroup defines the location of the measured potential with respect to the lipid bilayer interface. Electrostatic surface potentials measured by EPR of IMTSL-PTE show a remarkable (within ±2%) agreement with the Gouy-Chapman theory for anionic DMPG bilayers in fluid (48°C) phase at low electrolyte concentration (50 mM) and in gel (17°C) phase at 150-mM electrolyte concentration. This agreement begins to diminish for DMPG vesicles in gel phase (17°C) upon varying electrolyte concentration and fluid phase bilayers formed from DMPG/DMPC and POPG/POPC mixtures. Possible reasons for such deviations, as well as the proper choice of an electrostatically neutral reference interface, have been discussed. Described EPR method is expected to be fully applicable to more-complex models of cellular membranes.

  15. Lipid bilayers on nano-templates

    Science.gov (United States)

    Noy, Aleksandr; Artyukhin, Alexander B.; Bakajin, Olgica; Stoeve, Pieter

    2009-08-04

    A lipid bilayer on a nano-template comprising a nanotube or nanowire and a lipid bilayer around the nanotube or nanowire. One embodiment provides a method of fabricating a lipid bilayer on a nano-template comprising the steps of providing a nanotube or nanowire and forming a lipid bilayer around the polymer cushion. One embodiment provides a protein pore in the lipid bilayer. In one embodiment the protein pore is sensitive to specific agents

  16. Membrane order parameters for interdigitated lipid bilayers measured via polarized total-internal-reflection fluorescence microscopy.

    Science.gov (United States)

    Ngo, An T; Jakubek, Zygmunt J; Lu, Zhengfang; Joós, Béla; Morris, Catherine E; Johnston, Linda J

    2014-11-01

    Incorporating ethanol in lipid membranes leads to changes in bilayer structure, including the formation of an interdigitated phase. We have used polarized total-internal-reflection fluorescence microscopy (pTIRFM) to measure the order parameter for Texas Red DHPE incorporated in the ethanol-induced interdigitated phase (LβI) formed from ternary lipid mixtures comprising dioleoylphosphatidylcholine, cholesterol and egg sphingomyelin or dipalmitoylphosphatidylcholine. These lipid mixtures have 3 co-existing phases in the presence of ethanol: liquid-ordered, liquid-disordered and LβI. pTIRFM using Texas Red DHPE shows a reversal in fluorescence contrast between the LβI phase and the surrounding disordered phase with changes in the polarization angle. The contrast reversal is due to changes in the orientation of the dye, and provides a rapid method to identify the LβI phase. The measured order parameters for the LβI phase are consistent with a highly ordered membrane environment, similar to a gel phase. An acyl-chain labeled BODIPY-FL-PC was also tested for pTIRFM studies of ethanol-treated bilayers; however, this probe is less useful since the order parameters of the interdigitated phase are consistent with orientations that are close to random, either due to local membrane disorder or to a mixture of extended and looping conformations in which the fluorophore is localized in the polar headgroup region of the bilayer. In summary, we demonstrate that order parameter measurements via pTIRFM using Texas Red-DHPE can rapidly identify the interdigitated phase in supported bilayers. We anticipate that this technique will aid further research in the effects of alcohols and other additives on membranes.

  17. FRACTURE OF AMORPHOUS BILAYER RIBBON

    NARCIS (Netherlands)

    Ocelik, Vaclav; DUHAJ, P; CSACH, K; MISKUF, J; BENGUS, VZ

    On the basis of measuring the mechanical properties and observing the fracture surface of an amorphous bilayer ribbon some partial conclusions on the mechanical quality of the bimetal boundary were drawn.

  18. Impedance measurements of self-assembled lipid bilayer membranes on the tip of an electrode.

    Science.gov (United States)

    Bordi, F; Cametti, Cesare; Gliozzi, A

    2002-07-01

    Supported lipid membranes were self-assembled on the tip of a freshly cleaved silver wire, in the presence of an appropriate polarization voltage, to facilitate, during the membrane formation, the organization of the lipids into an ordered structure. Radiowave impedance spectroscopy measurements have been carried out to provide information on the relaxation properties of the system. We have measured the conductometric and dielectric properties of bilayers built up of different lipids [dipalmitoylphosphatidic acid (DPPA), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), linoleic acid (LIN)] in a wide frequency range (from 10(3) to 10(6) Hz) and in electrolyte solutions of different ionic strengths, in the presence of uni-univalent (KCl) and di-univalent (CaCl(2), MgCl(2), ZnCl(2)) electrolytes. This made it possible to measure the influence of different cations and different lipid compositions on the membrane properties. In particular, we have found a different capacitive behaviour of the supported lipid bilayer membrane (s-BLM) structure in the presence of different counterions in the electrolyte solution. This peculiarity offers the opportunity for the preparation of a variety of biosensors with diverse applications in membrane biophysics, biochemistry and biotechnology.

  19. Mechanisms of Action of (Methacrylates in Hemolytic Activity, in Vivo Toxicity and Dipalmitoylphosphatidylcholine (DPPC Liposomes Determined Using NMR Spectroscopy

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2012-01-01

    Full Text Available We investigated the quantitative structure-activity relationships between hemolytic activity (log 1/H50 or in vivo mouse intraperitoneal (ip LD50 using reported data for α,β-unsaturated carbonyl compounds such as (methacrylate monomers and their 13C-NMR β-carbon chemical shift (δ. The log 1/H50 value for methacrylates was linearly correlated with the δCβ value. That for (methacrylates was linearly correlated with log P, an index of lipophilicity. The ipLD50 for (methacrylates was linearly correlated with δCβ but not with log P. For (methacrylates, the δCβ value, which is dependent on the π-electron density on the β-carbon, was linearly correlated with PM3-based theoretical parameters (chemical hardness, η; electronegativity, χ; electrophilicity, ω, whereas log P was linearly correlated with heat of formation (HF. Also, the interaction between (methacrylates and DPPC liposomes in cell membrane molecular models was investigated using 1H-NMR spectroscopy and differential scanning calorimetry (DSC. The log 1/H50 value was related to the difference in chemical shift (ΔδHa (Ha: H (trans attached to the β-carbon between the free monomer and the DPPC liposome-bound monomer. Monomer-induced DSC phase transition properties were related to HF for monomers. NMR chemical shifts may represent a valuable parameter for investigating the biological mechanisms of action of (methacrylates.

  20. DMSO-Induced Dehydration of DPPC Membranes Studied by X-ray Diffraction, Small-Angle Neutron Scattering, and Calorimetry

    CERN Document Server

    Kiselev, M A; Kisselev, A M; Grabielle-Madelmond, C; Ollivon, M

    1999-01-01

    The influence of dimethyl sulfoxide (DMSO) on membrane thickness, multilamellar repeat distance, and phase transitions of 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) was investigated by X-ray diffraction and small-angle neutron scattering (SANS). The differential scanning calorimetry (DSC) study of water freezing and ice melting was performed in the ternary DPPC /DMSO /water and binary DMSO /water systems. The methods applied demonstrated the differences in membrane structure in three sub-regions of the DMSO mole fraction (X_dmso): from 0.0 to 0.3 for the first, from 0.3 to 0.8 for the second, and from 0.9 to 1.0 for the third sub-region. The thickness of the intermembrane solvent at T =20C decreases from 14.4 +/- 1.8 A at X_dmso =0.0 to 7.8 +/- 1.8 A at X_dmso =0.1. The data were used to determine the number of free water molecules in the intermembrane space in the presence of DMSO. The results for 0.0 < X_dmso < 0.3 were explained in the framework of DMSO-induced dehydration of the interme...

  1. Interfacial properties in Langmuir monolayers and LB films of DPPC with partially fluorinated alcohol (F8H7OH).

    Science.gov (United States)

    Nakahara, Hiromichi; Hirano, Chikayo; Fujita, Ichiro; Shibata, Osamu

    2013-01-01

    Two-component interactions between (perfluorooctyl) heptanol (F8H7OH) and dipalmitoylphosphatidylcholine (DPPC), which is a major component of pulmonary surfactants in mammals, were systematically elucidated using Langmuir monolayers and Langmuir-Blodgett (LB) films of the compounds. The interactions such as the miscibility of the compounds and their phase behavior were examined from thermodynamic and morphological perspectives. The surface pressure (π)-molecular area (A) and surface potential (ΔV)-A isotherms of the binary monolayers containing F8H7OH in different mole fractions (XF8H7OH) were measured simultaneously. The excess Gibbs free energy of mixing of the two components was calculated from the π-A isotherms. The resulting isotherm data were employed to construct a two-dimensional (2D) phase diagram of the system. The phase diagram revealed that the transition pressure as well as the monolayer collapse pressure change with changes in XF8H7OH. These thermodynamic analyses suggested that the miscibility of the two components and the solidification of DPPC monolayers can be induced by the addition of F8H7OH. The phase behavior upon monolayer compression was observed morphologically in situ using Brewster angle microscopy (BAM) and fluorescence microscopy (FM), as well as ex situ using atomic force microscopy (AFM). Interestingly, the AFM-based analysis revealed the formation of monodispersed 2D micelles consisting of F8H7OH at low surface pressures.

  2. The effect of tail-length mismatch in binary DMPC/DSPC lipid bilayers

    Science.gov (United States)

    Ashkar, Rana; Nagao, Michihiro; Butler, Paul

    2014-03-01

    Bilayer heterogeneity has been long hypothesized to drive raft formation and promote complex functionality in lipid membranes. The highly dynamic nature of the membrane however is thought to play a critical role in this delicate balance between structure and performance. To probe the effect of lateral heterogeneity on membrane dynamics, we investigate the thermal response of unilamellar-vesicle systems of mixed dimyristoylphosphatidylcholine (DMPC) and distearoylphosphatidylcholine (DSPC) with DMPC/DSPC ratios of 50/50 and 70/30. Both lipids experience a transition from an ordered gel phase, with stiff stretched tails, to a melted fluid phase, with more coiled flexible tails, as they are heated through their melting temperature, Tm(DMPC) ~ 21 °C and Tm(DSPC) ~ 51 °C. The distinct Tm's of the two lipids provide a broad gel-fluid phase with a significant mismatch (~ 20 Å) between the tail-lengths of the DMPC and DSPC molecules. The structural properties of the vesicles were determined by small-angle neutron and x-ray scattering and the collective lipid dynamics in the bilayer were investigated by neutron spin-echo (NSE) spectroscopy on selectively deuterated samples. The NSE results indicate a slowdown of thickness fluctuations in the gel-fluid coexistence phase and an intriguingly strong enhancement in the thickness fluctuation amplitude for T >Tm(DSPC) compared to our previous work on single component vesicles.

  3. Dynamics of bolaamphiphilic fluorescent polyenes in lipid bilayers from polarization emission spectroscopy.

    Science.gov (United States)

    Acuña, A Ulises; Amat-Guerri, Francisco; Quesada, Ernesto; Vélez, Marisela

    2006-06-20

    The rotational motions of the biamphiphilic polyenes (bolapolyenes) dimethyl all-(E)-octacosa-10,12,14,16,18-pentaenedioate (DE28:5) and dimethyl all-(E)-tetratriaconta-13,15,17,19,21-pentaenedioate (DE34:5), with head-to-head distances of 34 and 42A, respectively, have been examined by fluorescence anisotropy methods. The membrane-spanning bolapolyenes, which contain a central emitting pentaene group tethered to two methoxycarbonyl opposite polar heads by symmetric C(8) (DE28:5) and C(11) (DE34:5) polymethylene chains, were dispersed in lipid bilayers of DPPC or DMPC, and the stationary and picosecond-resolved emission was recorded as a function of temperature. In fluid-phase DMPC bilayers, three relaxation times could be determined, assigned to fast (0.2 and 2ns) single-bond isomerization processes localized on the alkyl chains, and to whole-molecule oscillations ( approximately 11ns), respectively. The anisotropy decay parameters were further analyzed in terms of a diffusive model for wobbling in a Gaussian ordering potential, to assess the anchoring effect of the symmetric polar heads. In this way, the average rotational diffusion constant of the bolapolyenes, D( perpendicular), could be estimated as 0.022-0.026rad(2) ns(-1) (DMPC bilayers, 35 degrees Celsius), a value that is only 1/3 of that corresponding to the related pentaene fatty acid spanning a single membrane monolayer. In contrast, the amplitude of the equilibrium orientational distribution (theta(half-cone) approximately 50 degrees ) is very similar for both the transmembrane and the single-headed polyenes. The reorientational oscillations of the central emitting group in the bolapolyenes necessarily would produce large-amplitude (2-5A) and very fast (ns) translational motions of the polar heads.

  4. Electromechanical oscillations in bilayer graphene

    Science.gov (United States)

    Benameur, Muhammed M.; Gargiulo, Fernando; Manzeli, Sajedeh; Autès, Gabriel; Tosun, Mahmut; Yazyev, Oleg V.; Kis, Andras

    2015-10-01

    Nanoelectromechanical systems constitute a class of devices lying at the interface between fundamental research and technological applications. Realizing nanoelectromechanical devices based on novel materials such as graphene allows studying their mechanical and electromechanical characteristics at the nanoscale and addressing fundamental questions such as electron-phonon interaction and bandgap engineering. In this work, we realize electromechanical devices using single and bilayer graphene and probe the interplay between their mechanical and electrical properties. We show that the deflection of monolayer graphene nanoribbons results in a linear increase in their electrical resistance. Surprisingly, we observe oscillations in the electromechanical response of bilayer graphene. The proposed theoretical model suggests that these oscillations arise from quantum mechanical interference in the transition region induced by sliding of individual graphene layers with respect to each other. Our work shows that bilayer graphene conceals unexpectedly rich and novel physics with promising potential in applications based on nanoelectromechanical systems.

  5. Monolayer compression induces fluidization in binary system of partially fluorinated alcohol (F4H11OH) with DPPC.

    Science.gov (United States)

    Nakahara, Hiromichi; Ohmine, Aya; Kai, Shoko; Shibata, Osamu

    2013-01-01

    A two-component Langmuir monolayer consisting of (perfluorobutyl)undecanol (F4H11OH) and dipalmitoylphosphatidylcholine (DPPC), a major component of pulmonary surfactants in mammals, has been investigated at the air-water interface. The binary monolayer has been systematically examined from both thermodynamic and morphological perspectives. The excess Gibbs free energy of mixing has been calculated from surface pressure (π)-molecular area (A) isotherms, and the results indicate that the miscibility of the two-component system shows a maximum in thermodynamical stability when the mole fraction (X(F4H11OH)) is 0.3. Results from a two-dimensional phase diagram (π vs. X(F4H11OH)) are consistent with these findings and depict the degree of miscibility resulting from the variation in the transition and collapse pressures relative to the concentration of X(F4H11OH). The miscibility is also supported by in situ Brewster angle microscopy and fluorescence microscopy, as well as ex situ atomic force microscopy for the system after transfer onto a mica substrate. Aside from temperature, a known driving force for the fluidization of DPPC monolayers is a change in surface composition caused by the addition of additive molecules. In the present study, however, the fluidization is driven by increasing surface pressures even at constant X(F4H11OH). Such a fluidization is a fascinating property when looked at in context of its potential implications for pulmonary replacement therapy, and hence, this study provides a fundamental insight into designing fluorinated materials for biomedical use.

  6. Dynamic molecular structure of DPPC-DLPC-cholesterol ternary lipid system by spin-label electron spin resonance.

    Science.gov (United States)

    Chiang, Yun-Wei; Shimoyama, Yuhei; Feigenson, Gerald W; Freed, Jack H

    2004-10-01

    The hydrated ternary lamellar lipid mixture of dipalmitoyl-PC/dilauroyl-PC/cholesterol (DPPC/DLPC/Chol) has been studied by electron spin resonance (ESR) to reveal the dynamic structure on a molecular level of the different phases that exist and coexist over virtually the full range of composition. The spectra for more than 100 different compositions at room temperature were analyzed by nonlinear least-squares fitting to provide the rotational diffusion rates and order parameters of the end-chain labeled phospholipid 16-PC. The ESR spectra exhibit substantial variation as a function of composition, even though the respective phases generally differ rather modestly from each other. The Lalpha and Lbeta phases are clearly distinguished, with the former exhibiting substantially lower ordering and greater motional rates, whereas the well-defined Lo phase exhibits the greatest ordering and relatively fast motional rates. Typically, smaller variations occur within a given phase. The ESR spectral analysis also yields phase boundaries and coexistence regions which are found to be consistent with previous results from fluorescence methods, although new features are found. Phase coexistence regions were in some cases confirmed by observing the existence of isosbestic points in the absorption mode ESR spectra from the phases. The dynamic structural properties of the DPPC-rich Lbeta and DLPC-rich Lalpha phases, within their two-phase coexistence region do not change with composition along a tie-line, but the ratio of the two phases follows the lever rule in accordance with thermodynamic principles. The analysis shows that 16-PC spin-label partitions nearly equally between the Lalpha and Lbeta phases, making it a useful probe for studying such coexisting phases. Extensive study of two-phase coexistence regions requires the determination of tie-lines, which were approximated in this study. However, a method is suggested to accurately determine the tie-lines by ESR.

  7. Effects of cholesterol on pore formation in lipid bilayers induced by human islet amyloid polypeptide fragments: A coarse-grained molecular dynamics study

    Science.gov (United States)

    Xu, Weixin; Wei, Guanghong; Su, Haibin; Nordenskiöld, Lars; Mu, Yuguang

    2011-11-01

    Disruption of the cellular membrane by the amyloidogenic peptide, islet amyloid polypeptide (IAPP), has been considered as one of the mechanisms of β-cell death during type 2 diabetes. The N-terminal region (residues 1-19) of the human version of IAPP is suggested to be primarily responsible for the membrane-disrupting effect of the full-length hIAPP peptide. However, the detailed assembly mode of hIAPP1-19 with membrane remains unclear. To gain insight into the interactions of hIAPP1-19 oligomer with the model membrane, we have employed coarse-grained molecular dynamics self-assembly simulations to study the aggregation of hIAPP1-19 fragments in the binary lipid made of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and anionic dipalmitoylphosphatidylserine (DPPS) in the presence and absence of different levels of cholesterol content. The membrane-destabilizing effect of hIAPP1-19 is found to be modulated by the presence of cholesterol. In the absence of cholesterol, hIAPP1-19 aggregates prefer to locate inside the bilayer, forming pore-like assemblies. While in the presence of cholesterol molecules, the lipid bilayer becomes more ordered and stiff, and the hIAPP1-19 aggregates are dominantly positioned at the bilayer-water interface. The action of cholesterol may suggest a possible way to maintain the membrane integrity by small molecule interference.

  8. Polydopamine-Supported Lipid Bilayers

    Directory of Open Access Journals (Sweden)

    Souryvanh Nirasay

    2012-12-01

    Full Text Available We report the formation of lipid membranes supported by a soft polymeric cushion of polydopamine. First, 20 nm thick polydopamine films were formed on mica substrates. Atomic force microscopy imaging indicated that these films were also soft with a surface roughness of 2 nm under hydrated conditions. A zwitterionic phospholipid bilayer was then deposited on the polydopamine cushion by fusion of dimyristoylphosphatidylcholine (DMPC and dioleoylphosphatidylcholine (DOPC vesicles. Polydopamine films preserved the lateral mobility of the phospholipids as shown by fluorescence microscopy recovery after photobleaching (FRAP experiments. Diffusion coefficients of ~5.9 and 7.2 µm2 s−1 were respectively determined for DMPC and DOPC at room temperature, values which are characteristic of lipids in a free standing bilayer system.

  9. Polydopamine-Supported Lipid Bilayers

    Science.gov (United States)

    Nirasay, Souryvanh; Badia, Antonella; Leclair, Grégoire; Claverie, Jerome P.; Marcotte, Isabelle

    2012-01-01

    We report the formation of lipid membranes supported by a soft polymeric cushion of polydopamine. First, 20 nm thick polydopamine films were formed on mica substrates. Atomic force microscopy imaging indicated that these films were also soft with a surface roughness of 2 nm under hydrated conditions. A zwitterionic phospholipid bilayer was then deposited on the polydopamine cushion by fusion of dimyristoylphosphatidylcholine (DMPC) and dioleoylphosphatidylcholine (DOPC) vesicles. Polydopamine films preserved the lateral mobility of the phospholipids as shown by fluorescence microscopy recovery after photobleaching (FRAP) experiments. Diffusion coefficients of ~5.9 and 7.2 µm2 s−1 were respectively determined for DMPC and DOPC at room temperature, values which are characteristic of lipids in a free standing bilayer system.

  10. Bilayer Effects of Antimalarial Compounds.

    Directory of Open Access Journals (Sweden)

    Nicole B Ramsey

    Full Text Available Because of the perpetual development of resistance to current therapies for malaria, the Medicines for Malaria Venture developed the Malaria Box to facilitate the drug development process. We tested the 80 most potent compounds from the box for bilayer-mediated effects on membrane protein conformational changes (a measure of likely toxicity in a gramicidin-based stopped flow fluorescence assay. Among the Malaria Box compounds tested, four compounds altered membrane properties (p< 0.05; MMV007384 stood out as a potent bilayer-perturbing compound that is toxic in many cell-based assays, suggesting that testing for membrane perturbation could help identify toxic compounds. In any case, MMV007384 should be approached with caution, if at all.

  11. Computer Simulations of Lipid Bilayers and Proteins

    DEFF Research Database (Denmark)

    Sonne, Jacob

    2006-01-01

    , Pressure profile calculations in lipid bilayers: A lipid bilayer is merely $\\sim$5~nm thick, but the lateral pressure (parallel to the bilayer plane) varies several hundred bar on this short distance (normal to the bilayer). These variations in the lateral pressure are commonly referred to as the pressure...... of neglecting pressure contributions from long range electrostatic interactions. The first issue is addressed by comparing two methods for calculating pressure profiles, and judged by the similar results obtained by these two methods the pressure profile appears to be well-defined for fluid phase lipid bilayers......The importance of computer simulations in lipid bilayer research has become more prominent for the last couple of decades and as computers get even faster, simulations will play an increasingly important part of understanding the processes that take place in and across cell membranes. This thesis...

  12. Horizontal Bilayer for Electrical and Optical Recordings

    Directory of Open Access Journals (Sweden)

    Alf Honigmann

    2012-12-01

    Full Text Available Artificial bilayer containing reconstituted ion channels, transporters and pumps serve as a well-defined model system for electrophysiological investigations of membrane protein structure–function relationship. Appropriately constructed microchips containing horizontally oriented bilayers with easy solution access to both sides provide, in addition, the possibility to investigate these model bilayer membranes and the membrane proteins therein with high resolution fluorescence techniques up to the single-molecule level. Here, we describe a bilayer microchip system in which long-term stable horizontal free-standing and hydrogel-supported bilayers can be formed and demonstrate its prospects particularly for single-molecule fluorescence spectroscopy and high resolution fluorescence microscopy in probing the physicochemical properties like phase behavior of the bilayer-forming lipids, as well as in functional studies of membrane proteins.

  13. Low-temperature sup 2 H NMR spectroscopy of phospholipid bilayers containing docosahexaenoyl (22:6. omega. 3) chains

    Energy Technology Data Exchange (ETDEWEB)

    Barry, J.A.; Trouard, T.P.; Salmon, A.; Brown, M.F. (Univ. of Arizona, Tucson (United States))

    1991-08-27

    Polyunsaturated fatty acids are widely distributed components of biological membranes and are believed to be involved in many biological functions. However, the mechanisms by which they act on a molecular level are not understood. To further investigate the unique properties of {omega}3 polyunsaturated phospholipid bilayers, deuterium nuclear ming tic resonance ({sup 2}H NMR) studies have been made of the liquid-crystalline (L{sub {alpha}}) and gel phases of a homologous series of mixed-chain phosphatidylcholines containing docosahexaenoic acid: (per-{sup 2}H-n:0) (22:6) PC, where n = 12, 14, 16, and 18. The moments of the {sup 2}H NMR lineshapes have been evaluated, and form these the warming and cooling main phase transition temperatures were determined. The transition temperatures of the mixed-chain series were found to be significantly lower ing those of the corresponding lipids in the disaturated series, di(per-{sup 2}H-n:0)PC, with hystereses ranging form 2 to 14 C. Distinct effects of the docosahexaenoyl chain on bilayer order were found, though these effects varied across the mixed-chain series. In evaluating the moment data, an empirical method for normalizing the moments with respect to differences in temperature was applied, in addition to using the reduced temperature method. For the systems studied here, the method of normalization haing significant effect on the interpretation of the moment data.

  14. DPPC/poly(2-methyl-2-oxazoline)-grad-poly(2-phenyl-2-oxazoline) chimeric nanostructures as potential drug nanocarriers

    Energy Technology Data Exchange (ETDEWEB)

    Pippa, Natassa [Faculty of Pharmacy, National and Kapodistrian University of Athens, Department of Pharmaceutical Technology (Greece); Kaditi, Eleni; Pispas, Stergios [Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation (Greece); Demetzos, Costas, E-mail: demetzos@pharm.uoa.gr [Faculty of Pharmacy, National and Kapodistrian University of Athens, Department of Pharmaceutical Technology (Greece)

    2013-06-15

    In this study, we report on the self assembly behavior and on stability studies of mixed (chimeric) nanosystems consisting of dipalmitoylphosphatidylcholine (DPPC) and poly(2-methyl-2-oxazoline)-grad-poly(2-phenyl-2-oxazoline) (MPOx) gradient copolymer in aqueous media and in fetal bovine serum (FBS). A gamut of light scattering techniques and fluorescence spectroscopy were used in order to extract information on the size and morphological characteristics of the nanoassemblies formed, as a function of gradient block copolymer content, as well as temperature. The hydrodynamic radii (R{sub h}) of nanoassemblies decreased in the process of heating up to 50 Degree-Sign C, while the fractal dimension (d{sub f}) values, also increased. Indomethacin was successfully incorporated into these chimeric nanocarriers. Drug release was depended on the components ratio. The present studies show that there are a number of parameters that can be used in order to alter the properties of chimeric nanosystems, and this is advantageous to the development of 'smart' nanocarriers for drug delivery.

  15. DPPC/poly(2-methyl-2-oxazoline)-grad-poly(2-phenyl-2-oxazoline) chimeric nanostructures as potential drug nanocarriers

    Science.gov (United States)

    Pippa, Natassa; Kaditi, Eleni; Pispas, Stergios; Demetzos, Costas

    2013-06-01

    In this study, we report on the self assembly behavior and on stability studies of mixed (chimeric) nanosystems consisting of dipalmitoylphosphatidylcholine (DPPC) and poly(2-methyl-2-oxazoline)-grad-poly(2-phenyl-2-oxazoline) (MPOx) gradient copolymer in aqueous media and in fetal bovine serum (FBS). A gamut of light scattering techniques and fluorescence spectroscopy were used in order to extract information on the size and morphological characteristics of the nanoassemblies formed, as a function of gradient block copolymer content, as well as temperature. The hydrodynamic radii ( R h) of nanoassemblies decreased in the process of heating up to 50 °C, while the fractal dimension ( d f) values, also increased. Indomethacin was successfully incorporated into these chimeric nanocarriers. Drug release was depended on the components ratio. The present studies show that there are a number of parameters that can be used in order to alter the properties of chimeric nanosystems, and this is advantageous to the development of "smart" nanocarriers for drug delivery.

  16. Superdiffusion in supported lipid bilayers

    CERN Document Server

    Campagnola, Grace; Schroder, Bryce W; Peersen, Olve B; Krapf, Diego

    2015-01-01

    We study the diffusion of membrane-targeting C2 domains using single-molecule tracking in supported lipid bilayers. The ensemble-averaged mean square displacement (MSD) exhibits superdiffusive behavior. However, the time-averaged MSD of individual trajectories is found to be linear with respect to lag time, as in Brownian diffusion. These observations are explained in terms of bulk excursions that introduce jumps with a heavy-tail distribution. Our experimental results are shown to agree with analytical models of bulk-mediated diffusion and with numerical simulations.

  17. Design, characterization, and aerosolization of organic solution advanced spray-dried moxifloxacin and ofloxacin dipalmitoylphosphatidylcholine (DPPC microparticulate/nanoparticulate powders for pulmonary inhalation aerosol delivery

    Directory of Open Access Journals (Sweden)

    Duan J

    2013-09-01

    Full Text Available Jinghua Duan,1,2 Frederick G Vogt,3 Xiaojian Li,1 Don Hayes Jr,4,5 Heidi M Mansour6 1University of Kentucky College of Pharmacy, Department of Pharmaceutical Sciences – Drug Development Division, Lexington, KY, USA; 2University of Washington-Seattle, College of Pharmacy, Department of Pharmaceutics, Seattle, WA, USA; 3GlaxoSmithKline, Analytical Sciences, Product Development, King of Prussia, PA, USA; 4The Ohio State University College of Medicine, Departments of Pediatrics and Internal Medicine, Nationwide Children's Hospital Lung and Heart-Lung Transplant Programs, Columbus, OH, USA; 5The Ohio State University, Davis Heart and Lung Research Institute, Columbus, OH, USA; 6The University of Arizona–Tucson, College of Pharmacy, Skaggs Center of Pharmaceutical Sciences, Tucson, AZ, USA Abstract: The aim of this study was to design and develop respirable antibiotics moxifloxacin (MOXI hydrochloride and ofloxacin (OFLX microparticles and nanoparticles, and multifunctional antibiotics particles with or without lung surfactant 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC for targeted dry powder inhalation delivery as a pulmonary nanomedicine. Particles were rationally designed and produced by advanced spray-drying particle engineering from an organic solution in closed mode (no water from dilute solution. Scanning electron microscopy indicated that these particles had both optimal particle morphology and surface morphology, and the particle size distributions were suitable for pulmonary delivery. Comprehensive and systematic physicochemical characterization and in vitro aerosol dispersion performance revealed significant differences between these two fluoroquinolone antibiotics following spray drying as drug aerosols and as cospray-dried antibiotic drug: DPPC aerosols. Fourier transform infrared spectroscopy and confocal Raman microspectroscopy were employed to probe composition and interactions in the solid state. Spray-dried MOXI was

  18. DNA nanotechnology: Bringing lipid bilayers into shape

    Science.gov (United States)

    Howorka, Stefan

    2017-07-01

    Lipid bilayers form the thin and floppy membranes that define the boundary of compartments such as cells. Now, a method to control the shape and size of bilayers using DNA nanoscaffolds has been developed. Such designer materials advance synthetic biology and could find use in membrane research.

  19. Fragmented state of lipid bilayers in water

    DEFF Research Database (Denmark)

    Helfrich, W.; Thimmel, J.; Klösgen, Beate Maria

    1999-01-01

    The bilayers of some typical biological membrane lipids such as PC and DGDG disintegrate in a large excess of water to form an optically invisible dispersive bilayer phase. `Dark bodies' can be reversibly precipitated from it by raising the temperature. The dispersive phase probably consists...

  20. Pseudocritical Behavior and Unbinding of Phospholipid Bilayers

    DEFF Research Database (Denmark)

    Lemmich, Jesper; Mortensen, Kell; Ipsen, John Hjorth;

    1995-01-01

    The temperature dependence of the small-angle neutron scattering from fully hydrated multilamellar phospholipid bilayers near the main phase transition is analyzed by means of a simple geometric model which yields both the lamellar repeat distance as well as the hydrophobic thickness of the bilayer...

  1. Alcohol's Effects on Lipid Bilayer Properties

    Science.gov (United States)

    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

  2. Planar bilayer membranes from photoactivable phospholipids.

    Science.gov (United States)

    Borle, F; Sänger, M; Sigrist, H

    1991-07-22

    Planar bilayer membranes formed from photoactivable phospholipids have been characterized by low frequency voltametry. Cyclic voltametric measurements were applied for simultaneous registration of planar membrane conductivity and capacitance. The procedure has been utilized to characterize the formation and stability of planar bilayer membranes. Bilayer membranes were formed from N'-(1,2-dimyristoyl-sn-glycero-3-phosphoethyl)-N-((m-3- trifluoromethyldiazirine)phenyl)thiourea (C14-PED), a head-group photosensitive phospholipid. In situ photoactivation of C14-PED at wavelengths greater than or equal to 320 nm altered neither the mean conductivity nor the capacitance of the bilayer. Ionophore (valinomycin) and ion channel (gramicidin) activities were not impaired upon photoactivation. In contrast, bilayer membranes formed from 1,2-bis(hexadeca-2,4-dienoyl)-sn- glycero-3-phosphocholine (C16-DENPC) revealed short life times. In situ photopolymerization of the diene fatty acids significantly increased the membrane conductivity or led to membrane rupture.

  3. Photon correlation spectroscopy of bilayer lipid membranes.

    Science.gov (United States)

    Crilly, J F; Earnshaw, J C

    1983-02-01

    Light scattering by thermal fluctuations on simple monoglyceride bilayer membranes has been used to investigate the viscoelastic properties of these structures. Spectroscopic analysis of these fluctuations (capillary waves) permits the nonperturbative measurement of the interfacial tension and a shear interfacial viscosity acting normal to the membrane plane. The methods were established by studies of solvent and nonsolvent bilayers of glycerol monooleate (GMO). Changes in the tension of GMO/n-decane membranes induced by altering the composition of the parent solution were detected and quantified. In a test of the reliability of the technique controlled variations of the viscosity of the aqueous bathing solution were accurately monitored. The technique was applied to solvent-free bilayers formed from dispersions of GMO in squalane. The lower tensions observed attested to the comparative absence of solvent in such bilayers. In contrast to the solvent case, the solvent-free membranes exhibited a significant transverse shear viscosity, indicative of the enhanced intermolecular interactions within the bilayer.

  4. "Nanocrystal bilayer for tandem catalysis"

    Energy Technology Data Exchange (ETDEWEB)

    Yamada, Yusuke; Tsung, Chia Kuang; Huang, Wenyu; Huo, Ziyang; E.Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Samorjai, Gabor A; Yang, Peidong

    2011-01-24

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO2-Pt and Pt-SiO2, can be used to catalyse two distinct sequential reactions. The CeO2-Pt interface catalysed methanol decomposition to produce CO and H2, which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO2 interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts

  5. Nanocrystal bilayer for tandem catalysis.

    Science.gov (United States)

    Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu; Huo, Ziyang; Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Somorjai, Gabor A; Yang, Peidong

    2011-05-01

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO(2)-Pt and Pt-SiO(2), can be used to catalyse two distinct sequential reactions. The CeO(2)-Pt interface catalysed methanol decomposition to produce CO and H(2), which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO(2) interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts.

  6. Multiscale Modeling of supported bilayers

    Science.gov (United States)

    Faller, Roland; Xing, Chenyue; Hoopes, Matthew I.

    2009-03-01

    Supported Lipid Bilayers are an abundant research platform for understanding the behavior of real cell membranes as they allow for additional mechanical stability. We studied systematically the changes that a support induces on a phospholipid bilayer using coarse-grained molecular modeling on different levels. We characterize the density and pressure profiles as well as the density imbalance inflicted on the membrane by the support. We also determine the diffusion coefficients and characterize the influence of different corrugations of the support. We then determine the free energy of transfer of phospholipids between the proximal and distal leaflet of a supported membrane using the coarse-grained Martini model. It turns out that there is at equilibrium about a 2-3% higher density in the proximal leaflet. These results are in favorable agreement with recent data obtained by very large scale modeling using a water free model where flip-flop can be observed directly. We compare results of the free energy of transfer obtained by pulling the lipid across the membrane in different ways. There are small quantitative differences but the overall picture is consistent. We are additionally characterizing the intermediate states which determine the barrier height and therefore the rate of translocation.

  7. Design, physicochemical characterization, and optimization of organic solution advanced spray-dried inhalable dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine poly(ethylene glycol) (DPPE-PEG) microparticles and nanoparticles for targeted respiratory nanomedicine delivery as dry powder inhalation aerosols.

    Science.gov (United States)

    Meenach, Samantha A; Vogt, Frederick G; Anderson, Kimberly W; Hilt, J Zach; McGarry, Ronald C; Mansour, Heidi M

    2013-01-01

    Novel advanced spray-dried and co-spray-dried inhalable lung surfactant-mimic phospholipid and poly(ethylene glycol) (PEG)ylated lipopolymers as microparticulate/nanoparticulate dry powders of biodegradable biocompatible lipopolymers were rationally formulated via an organic solution advanced spray-drying process in closed mode using various phospholipid formulations and rationally chosen spray-drying pump rates. Ratios of dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine PEG (DPPE-PEG) with varying PEG lengths were mixed in a dilute methanol solution. Scanning electron microscopy images showed the smooth, spherical particle morphology of the inhalable particles. The size of the particles was statistically analyzed using the scanning electron micrographs and SigmaScan® software and were determined to be 600 nm to 1.2 μm in diameter, which is optimal for deep-lung alveolar penetration. Differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) were performed to analyze solid-state transitions and long-range molecular order, respectively, and allowed for the confirmation of the presence of phospholipid bilayers in the solid state of the particles. The residual water content of the particles was very low, as quantified analytically via Karl Fischer titration. The composition of the particles was confirmed using attenuated total-reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and confocal Raman microscopy (CRM), and chemical imaging confirmed the chemical homogeneity of the particles. The dry powder aerosol dispersion properties were evaluated using the Next Generation Impactor™ (NGI™) coupled with the HandiHaler® dry powder inhaler device, where the mass median aerodynamic diameter from 2.6 to 4.3 μm with excellent aerosol dispersion performance, as exemplified by high values of emitted dose, fine particle fraction, and respirable fraction. Overall, it was determined that the pump rates defined in the

  8. Biotechnology Applications of Tethered Lipid Bilayer Membranes

    Directory of Open Access Journals (Sweden)

    Joshua A. Jackman

    2012-12-01

    Full Text Available The importance of cell membranes in biological systems has prompted the development of model membrane platforms that recapitulate fundamental aspects of membrane biology, especially the lipid bilayer environment. Tethered lipid bilayers represent one of the most promising classes of model membranes and are based on the immobilization of a planar lipid bilayer on a solid support that enables characterization by a wide range of surface-sensitive analytical techniques. Moreover, as the result of molecular engineering inspired by biology, tethered bilayers are increasingly able to mimic fundamental properties of natural cell membranes, including fluidity, electrical sealing and hosting transmembrane proteins. At the same time, new methods have been employed to improve the durability of tethered bilayers, with shelf-lives now reaching the order of weeks and months. Taken together, the capabilities of tethered lipid bilayers have opened the door to biotechnology applications in healthcare, environmental monitoring and energy storage. In this review, several examples of such applications are presented. Beyond the particulars of each example, the focus of this review is on the emerging design and characterization strategies that made these applications possible. By drawing connections between these strategies and promising research results, future opportunities for tethered lipid bilayers within the biotechnology field are discussed.

  9. Spin dynamics of bilayer manganites

    Indian Academy of Sciences (India)

    Tapan Chatterji

    2004-07-01

    The results of inelastic and quasi-elastic neutron scattering investigations on the 40% hole-doped quasi-2D bilayer manganites La1.2Sr1.8Mn2O7 have been reviewed. The complete set of exchange interactions have been determined on the basis of a localized Heisenberg model. However, the spin wave dispersion in La1.2Sr1.8Mn2O7 shows softening close to the zone boundary and are also heavily damped especially close to the zone boundary and deviate from that expected for a simple Heisenberg model. A minimal double exchange model including quantum corrections can reproduce these effects qualitatively but falls short of quantitative agreement.

  10. Bilayer-thickness-mediated interactions between integral membrane proteins

    CERN Document Server

    Kahraman, Osman; Klug, William S; Haselwandter, Christoph A

    2016-01-01

    Hydrophobic thickness mismatch between integral membrane proteins and the surrounding lipid bilayer can produce lipid bilayer thickness deformations. Experiment and theory have shown that protein-induced lipid bilayer thickness deformations can yield energetically favorable bilayer-mediated interactions between integral membrane proteins, and large-scale organization of integral membrane proteins into protein clusters in cell membranes. Within the continuum elasticity theory of membranes, the energy cost of protein-induced bilayer thickness deformations can be captured by considering compression and expansion of the bilayer hydrophobic core, membrane tension, and bilayer bending, resulting in biharmonic equilibrium equations describing the shape of lipid bilayers for a given set of bilayer-protein boundary conditions. Here we develop a combined analytic and numerical methodology for the solution of the equilibrium elastic equations associated with protein-induced lipid bilayer deformations. Our methodology al...

  11. Fragmented state of lipid bilayers in water

    DEFF Research Database (Denmark)

    Helfrich, W.; Thimmel, J.; Klösgen, Beate Maria

    1999-01-01

    The bilayers of some typical biological membrane lipids such as PC and DGDG disintegrate in a large excess of water to form an optically invisible dispersive bilayer phase. `Dark bodies' can be reversibly precipitated from it by raising the temperature. The dispersive phase probably consists...... of `knotted sticks', i.e. very thin nodular tubes of bilayer. After reviewing pertinent experimental and theoretical work we report on the discovery of a lower consolute point near room temperature in DGDG/water systems. Its existence shows that the dispersive phase and the dark bodies belong to the same...

  12. Berry phase transition in twisted bilayer graphene

    Science.gov (United States)

    Rode, Johannes C.; Smirnov, Dmitri; Schmidt, Hennrik; Haug, Rolf J.

    2016-09-01

    The electronic dispersion of a graphene bilayer is highly dependent on rotational mismatch between layers and can be further manipulated by electrical gating. This allows for an unprecedented control over electronic properties and opens up the possibility of flexible band structure engineering. Here we present novel magnetotransport data in a twisted bilayer, crossing the energetic border between decoupled monolayers and coupled bilayer. In addition a transition in Berry phase between π and 2π is observed at intermediate magnetic fields. Analysis of Fermi velocities and gate induced charge carrier densities suggests an important role of strong layer asymmetry for the observed phenomena.

  13. PLGA/DPPC/trimethylchitosan spray-dried microparticles for the nasal delivery of ropinirole hydrochloride: in vitro, ex vivo and cytocompatibility assessment

    Energy Technology Data Exchange (ETDEWEB)

    Karavasili, Christina [Laboratory of Pharmaceutical Technology, Department of Pharmacy, Aristotle University of Thessaloniki, 54124 (Greece); Bouropoulos, Nikolaos [Department of Materials Science, University of Patras, 26504 Rio, Patras (Greece); Foundation for Research and Technology, Hellas-Institute of Chemical Engineering and High Temperature, P.O. Box 1414, 26504 Patras (Greece); Sygellou, Lamprini [Foundation for Research and Technology, Hellas-Institute of Chemical Engineering and High Temperature, P.O. Box 1414, 26504 Patras (Greece); Amanatiadou, Elsa P.; Vizirianakis, Ioannis S. [Laboratory of Pharmacology, Department of Pharmaceutical Sciences, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Fatouros, Dimitrios G., E-mail: dfatouro@pharm.auth.gr [Laboratory of Pharmaceutical Technology, Department of Pharmacy, Aristotle University of Thessaloniki, 54124 (Greece)

    2016-02-01

    In the present study we investigated polymer-lipid microparticles loaded with ropinirole hydrochloride (RH) for nasal delivery. RH microparticles were further evaluated by means of scanning electron microscopy (SEM), ζ-potential measurements, Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD). In vitro release studies were performed in simulated nasal electrolyte solution (SNES) pH 5.5 at 35 °C. Ex vivo permeation studies were conducted across sheep nasal mucosa. Cytocompatibility was tested in cultured human airway epithelial cells (Calu-3). SEM studies revealed spheroid microparticles in the range of 2.09 μm to 2.41 μm. The presence of trimethylchitosan (TMC) induced a slight shift towards less negative ζ-potential values. Surface chemistry (XPS) revealed the presence of dipalmitoylphospatidylcholine (DPPC) and poly(lactic-co-glycolic acid) (PLGA) onto microparticles' surface, further corroborating the FT-IR and XRD findings. In vitro release studies showed that the microparticle composition can partly modulate the release of RH. Ex vivo studies demonstrated a 2.35-folded enhancement of RH permeation when RH was co-formulated with TMC of low molecular weight, compared to the control. All formulations tested were found to be non-toxic to cells. The results suggest that polymer-lipid microparticles may be a promising carrier for the nasal delivery of RH. - Highlights: • Development of microparticles comprising PLGA/DPPC/TMC for nasal drug delivery. • Physicochemical characterization showed that DPPC dominated microparticles' surface. • Microparticles enhanced permeation of ropinirole across sheep nasal epithelium. • The cytotoxicity assay with Calu-3 cells demonstrated satisfactory cell viability.

  14. Comparison of sorafenib-loaded poly (lactic/glycolic) acid and DPPC liposome nanoparticles in the in vitro treatment of renal cell carcinoma.

    Science.gov (United States)

    Liu, James; Boonkaew, Benjawan; Arora, Jaspreet; Mandava, Sree Harsha; Maddox, Michael M; Chava, Srinivas; Callaghan, Cameron; He, Jibao; Dash, Srikanta; John, Vijay T; Lee, Benjamin R

    2015-03-01

    The objective of this study is to develop and compare several Sorafenib-loaded biocompatible nanoparticle models in order to optimize drug delivery and tumor cellular kill thereby improving the quality of Sorafenib-regimented chemotherapy. Sorafenib-loaded poly (lactic-co-glycolic) acid (PLGA), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) liposomes, and hydrophobically modified chitosan (HMC)-coated DPPC liposomes were evaluated for several characteristics including zeta potential, drug loading, and release profile. Cytotoxicity and uptake trials were also studied using cell line RCC 786-0, a human metastatic clear cell histology renal cell carcinoma cell line. Sorafenib-loaded PLGA particles and HMC-coated DPPC liposomes exhibited significantly improved cell kill compared to Sorafenib alone at lower concentrations, namely 10-15 and 5-15 μM from 24 to 96 h, respectively. At maximum dosage and time (15 μM and 96 h), Sorafenib-loaded PLGA and HMC-coated liposomes killed 88.3 ± 1.8% and 98 ± 1.1% of all tumor cells, significant values compared with Sorafenib 81.8 ± 1.7% (p < 0.01). Likewise, HMC coating substantially improved cell kill for liposome model for all concentrations (5-15 μM) and at time points (24-96 h) (p < 0.01). PLGA and HMC-coated liposomes are promising platforms for drug delivery of Sorafenib. Because of different particle characteristics of PLGA and liposomes, each model can be further developed for unique clinical modalities.

  15. Dynamic Morphologies of Microscale Droplet Interface Bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Mruetusatorn, Prachya [ORNL; Boreyko, Jonathan B [ORNL; Sarles, Stephen A [ORNL; Venkatesan, Guru [The University of Tennessee; Hayes, Douglas G [ORNL; Collier, Pat [ORNL

    2014-01-01

    Droplet interface bilayers (DIBs) are a powerful platform for studying the dynamics of synthetic cellular membranes; however, very little has been done to exploit the unique dynamical features of DIBs. Here, we generate microscale droplet interface bilayers ( DIBs) by bringing together femtoliter-volume water droplets in a microfluidic oil channel, and characterize morphological changes of the DIBs as the droplets shrink due to evaporation. By varying the initial conditions of the system, we identify three distinct classes of dynamic morphology. (1) Buckling and Fission: When forming DIBs using the lipid-out method (lipids in oil phase), lipids in the shrinking monolayers continually pair together and slide into the bilayer to conserve their mass. As the bilayer continues to grow, it becomes confined, buckles, and eventually fissions one or more vesicles. (2) Uniform Shrinking: When using the lipid-in method (lipids in water phase) to form DIBs, lipids uniformly transfer from the monolayers and bilayer into vesicles contained inside the water droplets. (3) Stretching and Unzipping: Finally, when the droplets are pinned to the wall(s) of the microfluidic channel, the droplets become stretched during evaporation, culminating in the unzipping of the bilayer and droplet separation. These findings offer a better understanding of the dynamics of coupled lipid interfaces.

  16. Mechanisms of action of (meth)acrylates in hemolytic activity, in vivo toxicity and dipalmitoylphosphatidylcholine (DPPC) liposomes determined using NMR spectroscopy.

    Science.gov (United States)

    Fujisawa, Seiichiro; Kadoma, Yoshinori

    2012-01-01

    We investigated the quantitative structure-activity relationships between hemolytic activity (log 1/H(50)) or in vivo mouse intraperitoneal (ip) LD(50) using reported data for α,β-unsaturated carbonyl compounds such as (meth)acrylate monomers and their (13)C-NMR β-carbon chemical shift (δ). The log 1/H(50) value for methacrylates was linearly correlated with the δC(β) value. That for (meth)acrylates was linearly correlated with log P, an index of lipophilicity. The ipLD(50) for (meth)acrylates was linearly correlated with δC(β) but not with log P. For (meth)acrylates, the δC(β) value, which is dependent on the π-electron density on the β-carbon, was linearly correlated with PM3-based theoretical parameters (chemical hardness, η; electronegativity, χ; electrophilicity, ω), whereas log P was linearly correlated with heat of formation (HF). Also, the interaction between (meth)acrylates and DPPC liposomes in cell membrane molecular models was investigated using (1)H-NMR spectroscopy and differential scanning calorimetry (DSC). The log 1/H(50) value was related to the difference in chemical shift (ΔδHa) (Ha: H (trans) attached to the β-carbon) between the free monomer and the DPPC liposome-bound monomer. Monomer-induced DSC phase transition properties were related to HF for monomers. NMR chemical shifts may represent a valuable parameter for investigating the biological mechanisms of action of (meth)acrylates.

  17. RKKY interaction in bilayer graphene

    Science.gov (United States)

    Mohammadi, Yawar; Moradian, Rostam

    2015-12-01

    We study the RKKY interaction between two magnetic impurities located on the same layer (intralayer case) or on different layers (interlayer case) in undoped bilayer graphene (BLG) in the four-bands model, by directly calculating the Green functions in the eigenvalues and eigenvectors representation. Our results show that both intra- and interlayer RKKY interactions between two magnetic impurities located on the same (opposite) sublattice are always ferromagnetic (antiferromagnetic). Furthermore we find unusual long-distance decay of the RKKY interaction in BLG. The intralyer RKKY interactions between two magnetic impurities located on the same sublattice, J AnAn(R) and J BnBn(R), decay closely as 1 /R6 and 1 /R2 at large impurity distances respectively, but when they are located on opposite sublattices the RKKY interactions exhibit 1 /R4 decays approximately. In the interlayer case, the RKKY interactions between two magnetic impurities located on the same sublattice show a decay close to 1 /R4 at large impurity distances, but if two magnetic impurities be on opposite sublattices the RKKY interactions, J A1B2(R) and J B1A2(R), decay closely as 1 /R6 and 1 /R2 respectively. Both intra- and interlayer RKKY interactions have anisotropic oscillatory factors which for intralayer case is equal to that for single layer graphene (SLG). Our results at weak and strong interlayer coupling limits reduce to the RKKY interaction of SLG and that of BLG in the two-bands approximation respectively.

  18. Interactions of a lytic peptide with supported lipid bilayers investigated by time-resolved evanescent wave-induced fluorescence spectroscopy

    Science.gov (United States)

    Rapson, Andrew C.; Gee, Michelle L.; Clayton, Andrew H. A.; Smith, Trevor A.

    2016-12-01

    We report investigations, using time-resolved and polarised evanescent wave-induced fluorescence methods, into the location, orientation and mobility of a fluorescently labelled form of the antimicrobial peptide, melittin, when it interacts with vesicles and supported lipid bilayers (SLBs). This melittin analogue, termed MK14-A430, was found to penetrate the lipid headgroup structure in pure, ordered-phase DPPC membranes but was located near the headgroup-water region when cholesterol was included. MK14-A430 formed lytic pores in SLBs, and an increase in pore formation with incubation time was observed through an increase in polarity and mobility of the probe. When associated with the Cholesterol-containing SLB, the probe displayed polarity and mobility that indicated a population distributed near the lipid headgroup-water interface with MK14-A430 arranged predominantly in a surface-aligned state. This study indicates that the lytic activity of MK14-A430 occurred through a pore-forming mechanism. The lipid headgroup environment experienced by the fluorescent label, where MK14-A430 displayed pore information, indicated that pore formation was best described by the toroidal pore model.

  19. Super resolution microscopy of lipid bilayer phases and single molecule kinetic studies on merocyanine 540 bound lipid vesicles

    Science.gov (United States)

    Kuo, Chin-Kuei

    Recently, observing biological process and structural details in live cell became feasible after the introduction of super-resolution microscopy. Super-resolution microscopy by single molecule localization is the method that has commonly been used for such purpose. There are mainly three approaches to it: stochastic optical reconstruction microscopy (STORM), photoactivated localization microscopy (PALM), and point accumulation in nanoscale topology (PAINT). STORM and PALM rely on external laser control and use of photoactivable fluorescent protein or photoswitchable dyes and are technically challenging. The PAINT method relies on the control of thermal reaction rates to enable the switching between bright and dark states. Therefore, many conventional fluorescent probes can be applied in PAINT method and the images denote different information composed of interactions between the probe and its immediate environment by variations of probe parameters. The existence of lipid rafts has been under debates for decades due to the lack of a tool to directly visualize them in live cells. In the thesis, we combine PAINT with a phase sensitive dye, Merocyanine 540, to enable nanoscale observation of phase separation on supported lipid bilayers of mixed liquid/gel phases. The imaging results are presented in the chapter 3. Given that this is the first example of visualization of nanoscale phase separation of lipid bilayers using an optical microscope, we further looked into the kinetics of MC540 monomer dimer equilibrium in lipid bilayers using single molecule intensity time trajectory analysis and polarization dependent imaging. Our finding confirms that perpendicular monomeric MC540 (to the membrance surface) is the emitting speices in our system and it stays fluorescent for roughly 3 ms before it switches off to dark states. This part of analysis is presented in the chapter 4. All the materials, procedures to carry out experiments and data analysis, methods involved in our

  20. Piezoelectricity in asymmetrically strained bilayer graphene

    Science.gov (United States)

    Van der Donck, M.; De Beule, C.; Partoens, B.; Peeters, F. M.; Van Duppen, B.

    2016-09-01

    We study the electronic properties of commensurate faulted bilayer graphene by diagonalizing the one-particle Hamiltonian of the bilayer system in a complete basis of Bloch states of the individual graphene layers. Our novel approach is very general and can be easily extended to any commensurate graphene-based heterostructure. Here, we consider three cases: (i) twisted bilayer graphene, (ii) bilayer graphene where triaxial stress is applied to one layer and (iii) bilayer graphene where uniaxial stress is applied to one layer. We show that the resulting superstructures can be divided into distinct classes, depending on the twist angle or the magnitude of the induced strain. The different classes are distinguished from each other by the interlayer coupling mechanism, resulting in fundamentally different low-energy physics. For the cases of triaxial and uniaxial stress, the individual graphene layers tend to decouple and we find significant charge transfer between the layers. In addition, this piezoelectric effect can be tuned by applying a perpendicular electric field. Finally, we show how our approach can be generalized to multilayer systems.

  1. Residual stresses in bilayer dental ceramics.

    Science.gov (United States)

    Taskonak, Burak; Mecholsky, John J; Anusavice, Kenneth J

    2005-06-01

    It is clinically observed that lithia-disilicate-based all-ceramic fixed partial dentures (FPD) can fail because of the fragmentation of the veneering material. The hypothesis of this study is that the global residual stresses within the surface of those veneered FPDs may be responsible for partial fragmentation of the veneering ceramic. Bilayer and monolithic ceramic composites were prepared using a lithia disilicate based (Li2OSiO2) glass-ceramic core and a glass veneer. A four-step fracture mechanics approach was used to analyze residual stress in bilayered all-ceramic FPDs. We found a statistically significant increase in the mean flexural strengths of bilayer specimens compared with monolithic glass specimens (p < or = 0.05). There was a statistically significant difference between the mean longitudinal and transverse indentation-induced crack sizes in bilayer specimens (p < or = 0.05), which indicates the existence of residual stress. Global residual stresses in the veneer layer, calculated using a fracture mechanics equation, were determined to be responsible for the increased strength and observed chipping, i.e., spallation in bilayer ceramic composites.

  2. Viscoelastic deformation of lipid bilayer vesicles†

    Science.gov (United States)

    Wu, Shao-Hua; Sankhagowit, Shalene; Biswas, Roshni; Wu, Shuyang; Povinelli, Michelle L.

    2015-01-01

    Lipid bilayers form the boundaries of the cell and its organelles. Many physiological processes, such as cell movement and division, involve bending and folding of the bilayer at high curvatures. Currently, bending of the bilayer is treated as an elastic deformation, such that its stress-strain response is independent of the rate at which bending strain is applied. We present here the first direct measurement of viscoelastic response in a lipid bilayer vesicle. We used a dual-beam optical trap (DBOT) to stretch 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) giant unilamellar vesicles (GUVs). Upon application of a step optical force, the vesicle membrane deforms in two regimes: a fast, instantaneous area increase, followed by a much slower stretching to an eventual plateau deformation. From measurements of dozens of GUVs, the average time constant of the slower stretching response was 0.225 ± 0.033 s (standard deviation, SD). Increasing the fluid viscosity did not affect the observed time constant. We performed a set of experiments to rule out heating by laser absorption as a cause of the transient behavior. Thus, we demonstrate here that the bending deformation of lipid bilayer membranes should be treated as viscoelastic. PMID:26268612

  3. Viscoelastic deformation of lipid bilayer vesicles.

    Science.gov (United States)

    Wu, Shao-Hua; Sankhagowit, Shalene; Biswas, Roshni; Wu, Shuyang; Povinelli, Michelle L; Malmstadt, Noah

    2015-10-07

    Lipid bilayers form the boundaries of the cell and its organelles. Many physiological processes, such as cell movement and division, involve bending and folding of the bilayer at high curvatures. Currently, bending of the bilayer is treated as an elastic deformation, such that its stress-strain response is independent of the rate at which bending strain is applied. We present here the first direct measurement of viscoelastic response in a lipid bilayer vesicle. We used a dual-beam optical trap (DBOT) to stretch 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) giant unilamellar vesicles (GUVs). Upon application of a step optical force, the vesicle membrane deforms in two regimes: a fast, instantaneous area increase, followed by a much slower stretching to an eventual plateau deformation. From measurements of dozens of GUVs, the average time constant of the slower stretching response was 0.225 ± 0.033 s (standard deviation, SD). Increasing the fluid viscosity did not affect the observed time constant. We performed a set of experiments to rule out heating by laser absorption as a cause of the transient behavior. Thus, we demonstrate here that the bending deformation of lipid bilayer membranes should be treated as viscoelastic.

  4. Magnetoacoustic resonance in magnetoelectric bilayers

    Science.gov (United States)

    Filippov, D. A.; Bichurin, M. I.; Petrov, V. M.; Srinivasan, G.

    2004-03-01

    Layered composites of ferrite and ferroelectric single crystal thin films are of interest for studies on magnetoelectric interactions [1,2]. Such interactions result in unique and novel effects that are absent in single phase materials. For example, in a single crystal composite it is possible to control the ferromagnetic resonance (FMR) parameters for the ferrite by means of hypersonic oscillations induced in the ferroelectric phase. The absorption of acoustic oscillations by the ferrite results in variation in FMR line shape and power absorbed. One anticipates resonance absorption of elastic waves when the frequency of elastic waves coincides with the precession frequency of magnetization vector. This work is concerned with the nature of FMR under the influence of acoustic oscillations with the same frequency as FMR. Bilayers of ferrite and piezoelectric single crystals are considered. Hypersonic waves induced in the piezoelectric phase transmit acoustic power into ferrite due to mechanical connectivity between the phases. That transmission depends strongly on interface coupling [3]. We estimate the resulting variations in ferromagnetic resonance line shape. Estimates of magnetoelectric effect at magnetoacoustic resonance are also given. In addition, dependence of absorption of acoustic power on sample dimensions and compliances, electric and magnetic susceptibilities, piezoelectric and magnetostriction coefficients is discussed. The theory provided here is important for an understanding of interface coupling and the nature of magnetoelastic interactions in the composites. 1. M. I. Bichurin and V. M. Petrov, Zh. Tekh. Fiz. 58, 2277 (1988) [Sov. Phys. Tech. Phys. 33, 1389 (1988)]. 2. M.I. Bichurin, I. A. Kornev, V. M. Petrov, A. S. Tatarenko, Yu. V. Kiliba, and G. Srinivasan. Phys. Rev. B 64, 094409 (2001). 3. M. I. Bichurin, V. M. Petrov, and G. Srinivasan, J. Appl. Phys. 92, 7681 (2002). This work was supported by grants from the Russian Ministry of Education (

  5. Solid-state NMR spectroscopy of a membrane protein in biphenyl phospholipid bicelles with the bilayer normal parallel to the magnetic field

    Science.gov (United States)

    Park, Sang Ho; Loudet, Cécile; Marassi, Francesca M.; Dufourc, Erick J.; Opella, Stanley J.

    2008-07-01

    Bicelles composed of the long-chain biphenyl phospholipid TBBPC (1-tetradecanoyl-2-(4-(4-biphenyl)butanoyl)-sn-glycero-3-PC) and the short-chain phospholipid DHPC align with their bilayer normals parallel to the direction of the magnetic field. In contrast, in typical bicelles the long-chain phospholipid is DMPC or DPPC, and the bilayers align with their normals perpendicular to the field. Samples of the membrane-bound form of the major coat protein of Pf1 bacteriophage in TBBPC bicelles are stable for several months, align magnetically over a wide range of temperatures, and yield well-resolved solid-state NMR spectra similar to those obtained from samples aligned mechanically on glass plates or in DMPC bicelle samples "flipped" with lanthanide ions so that their bilayer normals are parallel to the field. The order parameter of the TBBPC bicelle sample decreases from approximately 0.9 to 0.8 upon increasing the temperature from 20 °C to 60 °C. Since the frequency spans of the chemical shift and dipolar coupling interactions are twice as large as those obtained from proteins in DMPC bicelles without lanthanide ions, TBBPC bicelles provide an opportunity for structural studies with higher spectral resolution of the metal-binding membrane proteins without the risk of chemical or spectroscopic interference from the added lanthanide ions. In addition, the large temperature range of these samples is advantageous for the studies of membrane proteins that are unstable at elevated temperatures and for experiments requiring measurements as a function of temperature.

  6. Possible mechanism of adhesion in a mica supported phospholipid bilayer

    Energy Technology Data Exchange (ETDEWEB)

    Pertsin, Alexander, E-mail: ig3@ix.urz.uni-heidelberg.de [Angewandte Physikalische Chemie, Universität Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg (Germany); Institute of Organo-Element Compounds, Russian Academy of Sciences, Vavilov Str. 28, 117991 Moscow (Russian Federation); Grunze, Michael [Angewandte Physikalische Chemie, Universität Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg (Germany); Institute for Functional Interfaces, Karlsruhe Institute of Technology, Hermann-von- Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen (Germany)

    2014-05-14

    Phospholipid bilayers supported on hydrophilic solids like silica and mica play a substantial role in fundamental studies and technological applications of phospholipid membranes. In both cases the molecular mechanism of adhesion between the bilayer and the support is of primary interest. Since the possibilities of experimental methods in this specific area are rather limited, the methods of computer simulation acquire great importance. In this paper we use the grand canonical Monte Carlo technique and an atomistic force field to simulate the behavior of a mica supported phospholipid bilayer in pure water as a function of the distance between the bilayer and the support. The simulation reveals a possible adhesion mechanism, where the adhesion is due to individual lipid molecules that protrude from the bilayer and form widely spaced links with the support. Simultaneously, the bilayer remains separated from the bilayer by a thin water interlayer which maintains the bilayer fluidity.

  7. Ionic motion in PEDOT and PPy conducting polymer bilayers

    DEFF Research Database (Denmark)

    Zainudeen, Umer L.; Skaarup, Steen

    2006-01-01

    Conducting polymer bilayers with poly(3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole (PPy), each containing dodecyl benzenesulfonate (DBS) as immobile dopant species, were synthesized galvanostatically. The electrochemical behaviour of the bilayers was investigated using cyclic voltammetry...

  8. Ionic motion in PEDOT and PPy conducting polymer bilayers

    DEFF Research Database (Denmark)

    Zainudeen, Umer L.; Skaarup, Steen

    2006-01-01

    Conducting polymer bilayers with poly(3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole (PPy), each containing dodecyl benzenesulfonate (DBS) as immobile dopant species, were synthesized galvanostatically. The electrochemical behaviour of the bilayers was investigated using cyclic voltammetry...

  9. Design of Asymmetric Peptide Bilayer Membranes.

    Science.gov (United States)

    Li, Sha; Mehta, Anil K; Sidorov, Anton N; Orlando, Thomas M; Jiang, Zhigang; Anthony, Neil R; Lynn, David G

    2016-03-16

    Energetic insights emerging from the structural characterization of peptide cross-β assemblies have enabled the design and construction of robust asymmetric bilayer peptide membranes. Two peptides differing only in their N-terminal residue, phosphotyrosine vs lysine, coassemble as stacks of antiparallel β-sheets with precisely patterned charged lattices stabilizing the bilayer leaflet interface. Either homogeneous or mixed leaflet composition is possible, and both create nanotubes with dense negative external and positive internal solvent exposed surfaces. Cross-seeding peptide solutions with a preassembled peptide nanotube seed leads to domains of different leaflet architecture within single nanotubes. Architectural control over these cross-β assemblies, both across the bilayer membrane and along the nanotube length, provides access to highly ordered asymmetric membranes for the further construction of functional mesoscale assemblies.

  10. Capacitance Variation of Electrolyte-Gated Bilayer Graphene Based Transistors

    OpenAIRE

    Hediyeh Karimi; Rubiyah Yusof; Mohammad Taghi Ahmadi; Mehdi Saeidmanesh; Meisam Rahmani; Elnaz Akbari; Wong King Kiat

    2013-01-01

    Quantum capacitance of electrolyte-gated bilayer graphene field-effect transistors is investigated in this paper. Bilayer graphene has received huge attention due to the fact that an energy gap could be opened by chemical doping or by applying external perpendicular electric field. So, this extraordinary property can be exploited to use bilayer graphene as a channel in electrolyte-gated field-effect transistors. The quantum capacitance of bi-layer graphene with an equivalent circuit is presen...

  11. Temperature-dependent drug release from DPPC:C12H25-PNIPAM-COOH liposomes: control of the drug loading/release by modulation of the nanocarriers' components.

    Science.gov (United States)

    Pippa, Natassa; Meristoudi, Anastasia; Pispas, Stergios; Demetzos, Costas

    2015-05-15

    Novel polymer-modified thermosensitive liposomes were developed for the delivery of indomethacin in order to control its release profile. When attached to 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) liposomes, the end functionalized C12H25-poly(N-isopropylacrylamide)-COOH (C12H25-PNIPAM-COOH) polymer was membrane-disruptive in a temperature-dependent manner. The interest for this polymer is driven by its famous lower critical solution temperature (LCST) behavior, where heating an aqueous solution of PNIPAM above 32°C induces nanophase separation and polymer chain aggregation. The physicochemical/structural behavior of these polymer-modified thermosensitive liposomes was found to depend on the PNIPAM:lipid molar ratio and the composition of the polymeric guest. The incorporation of PNIPAM has caused alterations in the thermotropic behavior of DPPC liposomes, as the differential scanning calorimetry (DSC) experiments revealed. The drug loading and the release were found to be strongly dependent on the thermotropic characteristics of the PNIPAM grafted DPPC liposomes. Namely, the in vitro release is immediate at 37°C (>LCST) ("burst" effect), while the prepared mixed nanocarriers did not release the encapsulated bioactive substance at <32°C (DPPC/PNIPAM components, as well as the molecular characteristics of the polymeric guest.

  12. Bilayer graphene quantum dot defined by topgates

    Energy Technology Data Exchange (ETDEWEB)

    Müller, André; Kaestner, Bernd; Hohls, Frank; Weimann, Thomas; Pierz, Klaus; Schumacher, Hans W., E-mail: hans.w.schumacher@ptb.de [Physikalisch-Technische Bundesanstalt, Bundesallee 100, 38116 Braunschweig (Germany)

    2014-06-21

    We investigate the application of nanoscale topgates on exfoliated bilayer graphene to define quantum dot devices. At temperatures below 500 mK, the conductance underneath the grounded gates is suppressed, which we attribute to nearest neighbour hopping and strain-induced piezoelectric fields. The gate-layout can thus be used to define resistive regions by tuning into the corresponding temperature range. We use this method to define a quantum dot structure in bilayer graphene showing Coulomb blockade oscillations consistent with the gate layout.

  13. Temperature effect on plasmons in bilayer graphene

    Energy Technology Data Exchange (ETDEWEB)

    Patel, Digish K., E-mail: jdiggish@gmail.com; Sharma, A. C. [Physics Department, Faculty of Science, The M.S. University of Baroda, Vadodara-390002, Gujarat (India); Ashraf, S. S. Z. [Physics Department, Faculty of Science, Aligarh Muslim University, Aligarh-202002, Uttar Pradesh (India); Ambavale, S. K. [Vishwakarma Government Engineering College Chandkheda, Ahmedabad-382424, Gujarat (India)

    2015-06-24

    We have theoretically investigated the plasmon dispersion and damping rate of doped bilayer graphene (BLG) at finite temperatures within the random phase approximation. Our computed results on plasmon dispersion show that plasmon frequency enhances with increasing temperatures in contrast to single layer graphene where it is suppressed. This can be attributed to the fact that the dynamic response of the electron gas or screening in bilayer graphene is different from that of single layer graphene. Further the temperature effect on damping rate is also discussed.

  14. Electronic properties of graphene-based bilayer systems

    Energy Technology Data Exchange (ETDEWEB)

    Rozhkov, A.V., E-mail: arozhkov@gmail.com [CEMS, RIKEN, Saitama 351-0198 (Japan); Institute for Theoretical and Applied Electrodynamics, Russian Academy of Sciences, 125412 Moscow (Russian Federation); Moscow Institute of Physics and Technology, Dolgoprudny, Moscow Region, 141700 (Russian Federation); Sboychakov, A.O. [CEMS, RIKEN, Saitama 351-0198 (Japan); Institute for Theoretical and Applied Electrodynamics, Russian Academy of Sciences, 125412 Moscow (Russian Federation); Rakhmanov, A.L. [CEMS, RIKEN, Saitama 351-0198 (Japan); Institute for Theoretical and Applied Electrodynamics, Russian Academy of Sciences, 125412 Moscow (Russian Federation); Moscow Institute of Physics and Technology, Dolgoprudny, Moscow Region, 141700 (Russian Federation); All-Russia Research Institute of Automatics, Moscow, 127055 (Russian Federation); Nori, Franco, E-mail: fnori@riken.jp [CEMS, RIKEN, Saitama 351-0198 (Japan); Physics Department, The University of Michigan, Ann Arbor, MI 48109-1040 (United States)

    2016-08-23

    This article reviews the theoretical and experimental work related to the electronic properties of bilayer graphene systems. Three types of bilayer stackings are discussed: the AA, AB, and twisted bilayer graphene. This review covers single-electron properties, effects of static electric and magnetic fields, bilayer-based mesoscopic systems, spin–orbit coupling, dc transport and optical response, as well as spontaneous symmetry violation and other interaction effects. The selection of the material aims to introduce the reader to the most commonly studied topics of theoretical and experimental research in bilayer graphene.

  15. Electronic properties of graphene-based bilayer systems

    Science.gov (United States)

    Rozhkov, A. V.; Sboychakov, A. O.; Rakhmanov, A. L.; Nori, Franco

    2016-08-01

    This article reviews the theoretical and experimental work related to the electronic properties of bilayer graphene systems. Three types of bilayer stackings are discussed: the AA, AB, and twisted bilayer graphene. This review covers single-electron properties, effects of static electric and magnetic fields, bilayer-based mesoscopic systems, spin-orbit coupling, dc transport and optical response, as well as spontaneous symmetry violation and other interaction effects. The selection of the material aims to introduce the reader to the most commonly studied topics of theoretical and experimental research in bilayer graphene.

  16. Design, physicochemical characterization, and optimization of organic solution advanced spray-dried inhalable dipalmitoylphosphatidylcholine (DPPC and dipalmitoylphosphatidylethanolamine poly(ethylene glycol (DPPE-PEG microparticles and nanoparticles for targeted respiratory nanomedicine delivery as dry powder inhalation aerosols

    Directory of Open Access Journals (Sweden)

    Meenach SA

    2013-01-01

    Full Text Available Samantha A Meenach,1,2 Frederick G Vogt,3 Kimberly W Anderson,2,4 J Zach Hilt,2,4 Ronald C McGarry,5Heidi M Mansour1,41Department of Pharmaceutical Sciences-Drug Development Division, University of Kentucky College of Pharmacy, Lexington, KY; 2Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY, USA; 3Analytical Sciences, Product Development, GlaxoSmithKline, King of Prussia, PA; 4Center of Membrane Sciences, University of Kentucky, Lexington, KY, 5Department of Radiation Medicine, University of Kentucky College of Medicine, Lexington, KY, USAAbstract: Novel advanced spray-dried and co-spray-dried inhalable lung surfactant-mimic phospholipid and poly(ethylene glycol (PEGylated lipopolymers as microparticulate/nanoparticulate dry powders of biodegradable biocompatible lipopolymers were rationally formulated via an organic solution advanced spray-drying process in closed mode using various phospholipid formulations and rationally chosen spray-drying pump rates. Ratios of dipalmitoylphosphatidylcholine (DPPC and dipalmitoylphosphatidylethanolamine PEG (DPPE-PEG with varying PEG lengths were mixed in a dilute methanol solution. Scanning electron microscopy images showed the smooth, spherical particle morphology of the inhalable particles. The size of the particles was statistically analyzed using the scanning electron micrographs and SigmaScan® software and were determined to be 600 nm to 1.2 μm in diameter, which is optimal for deep-lung alveolar penetration. Differential scanning calorimetry (DSC and powder X-ray diffraction (PXRD were performed to analyze solid-state transitions and long-range molecular order, respectively, and allowed for the confirmation of the presence of phospholipid bilayers in the solid state of the particles. The residual water content of the particles was very low, as quantified analytically via Karl Fischer titration. The composition of the particles was confirmed using attenuated

  17. Electronic properties of a biased graphene bilayer

    Energy Technology Data Exchange (ETDEWEB)

    Castro, Eduardo V; Lopes dos Santos, J M B [CFP and Departamento de Fisica, Faculdade de Ciencias Universidade do Porto, P-4169-007 Porto (Portugal); Novoselov, K S; Morozov, S V; Geim, A K [Department of Physics and Astronomy, University of Manchester, Manchester M13 9PL (United Kingdom); Peres, N M R [Centre of Physics and Departamento de Fisica, Universidade do Minho, P-4710-057 Braga (Portugal); Nilsson, Johan; Castro Neto, A H [Department of Physics, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (United States); Guinea, F [Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco, E-28049 Madrid (Spain)

    2010-05-05

    We study, within the tight-binding approximation, the electronic properties of a graphene bilayer in the presence of an external electric field applied perpendicular to the system-a biased bilayer. The effect of the perpendicular electric field is included through a parallel plate capacitor model, with screening correction at the Hartree level. The full tight-binding description is compared with its four-band and two-band continuum approximations, and the four-band model is shown to always be a suitable approximation for the conditions realized in experiments. The model is applied to real biased bilayer devices, made out of either SiC or exfoliated graphene, and good agreement with experimental results is found, indicating that the model is capturing the key ingredients, and that a finite gap is effectively being controlled externally. Analysis of experimental results regarding the electrical noise and cyclotron resonance further suggests that the model can be seen as a good starting point for understanding the electronic properties of graphene bilayer. Also, we study the effect of electron-hole asymmetry terms, such as the second-nearest-neighbour hopping energies t' (in-plane) and {gamma}{sub 4} (inter-layer), and the on-site energy {Delta}.

  18. Electronic properties of a biased graphene bilayer.

    Science.gov (United States)

    Castro, Eduardo V; Novoselov, K S; Morozov, S V; Peres, N M R; Lopes dos Santos, J M B; Nilsson, Johan; Guinea, F; Geim, A K; Castro Neto, A H

    2010-05-01

    We study, within the tight-binding approximation, the electronic properties of a graphene bilayer in the presence of an external electric field applied perpendicular to the system-a biased bilayer. The effect of the perpendicular electric field is included through a parallel plate capacitor model, with screening correction at the Hartree level. The full tight-binding description is compared with its four-band and two-band continuum approximations, and the four-band model is shown to always be a suitable approximation for the conditions realized in experiments. The model is applied to real biased bilayer devices, made out of either SiC or exfoliated graphene, and good agreement with experimental results is found, indicating that the model is capturing the key ingredients, and that a finite gap is effectively being controlled externally. Analysis of experimental results regarding the electrical noise and cyclotron resonance further suggests that the model can be seen as a good starting point for understanding the electronic properties of graphene bilayer. Also, we study the effect of electron-hole asymmetry terms, such as the second-nearest-neighbour hopping energies t' (in-plane) and γ(4) (inter-layer), and the on-site energy Δ.

  19. Lipid bilayer composition influences small multidrug transporters

    Directory of Open Access Journals (Sweden)

    Curnow Paul

    2008-11-01

    Full Text Available Abstract Background Membrane proteins are influenced by their surrounding lipids. We investigate the effect of bilayer composition on the membrane transport activity of two members of the small multidrug resistance family; the Escherichia coli transporter, EmrE and the Mycobacterium tuberculosis, TBsmr. In particular we address the influence of phosphatidylethanolamine and anionic lipids on the activity of these multidrug transporters. Phosphatidylethanolamine lipids are native to the membranes of both transporters and also alter the lateral pressure profile of a lipid bilayer. Lipid bilayer lateral pressures affect membrane protein insertion, folding and activity and have been shown to influence reconstitution, topology and activity of membrane transport proteins. Results Both EmrE and TBsmr are found to exhibit a similar dependence on lipid composition, with phosphatidylethanolamine increasing methyl viologen transport. Anionic lipids also increase transport for both EmrE and TBsmr, with the proteins showing a preference for their most prevalent native anionic lipid headgroup; phosphatidylglycerol for EmrE and phosphatidylinositol for TBsmr. Conclusion These findings show that the physical state of the membrane modifies drug transport and that substrate translocation is dependent on in vitro lipid composition. Multidrug transport activity seems to respond to alterations in the lateral forces exerted upon the transport proteins by the bilayer.

  20. Localized plasmons in bilayer graphene nanodisks

    DEFF Research Database (Denmark)

    Wang, Weihua; Xiao, Sanshui; Mortensen, N. Asger

    2016-01-01

    We study localized plasmonic excitations in bilayer graphene (BLG) nanodisks, comparing AA-stacked and AB-stacked BLG and contrasting the results to the case of two monolayers without electronic hybridization. The electrodynamic response of the BLG electron gas is described in terms of a spatially...

  1. Capillary wrinkling of thin bilayer polymeric sheets

    Science.gov (United States)

    Chang, Jooyoung; Menon, Narayanan; Russell, Thomas

    We have investigated capillary force induced wrinkling on a floated polymeric bilayer thin sheet. The origin of the wrinkle pattern is compressional hoop stress caused by the capillary force of a water droplet placed on the floated polymeric thin sheet afore investigated. Herein, we study the effect of the differences of surface energy arising from the hydrophobicity of Polystyrene (PS Mw: 97 K, Contact Angle: 88 º) and the hydrophilicity of Poly(methylmethacrylate) (PMMA Mw: 99K, Contact Angle: 68 º) on two sides of a bilayer film. We measure the number and the length of the wrinkles by broadly varying the range of thicknesses of top (9 nm to 550 nm) and bottom layer (25 nm to 330 nm). At the same, there is only a small contrast in mechanical properties of the two layers (PS E = 3.4 GPa, and PMMA E = 3 GPa). The number of the wrinkles is not strongly affected by the composition (PS(Top)/PMMA(Bottom) or PMMA(Top)/PS(Bottom)) and the thickness of each and overall bilayer system. However, the length of the wrinkle is governed by the contact angle of the drop on the top layer of bilayer system. We also compare this to the wrinkle pattern obtained in monolayer systems over a wide range of thickness from PS and PMMA (7 nm to 1 μm). W.M. Keck Foundation.

  2. Bilayer Tablet via Microsphere: A Review

    Directory of Open Access Journals (Sweden)

    Piyushkumar Vinubhai Gundaraniya

    2013-01-01

    Full Text Available The aim of the present work is to develop bilayer tablets containing sustained release microspheres as one layer and immediate release as another layer. The proposed dosage form is intended to decrease the dosing frequency and the combined administration of an anti-diabetic agent. Several pharmaceutical companies are currently developing bi-layer tablets, for a variety of reasons: patent extension, therapeutic, marketing to name a few. To reduce capital investment, quite often existing but modified tablet presses are used to develop and produce such tablets. One such approach is using microspheres as carriers for drugs also known as micro particles. It is the reliable means to deliver the drug to the target site with specificity, if modified, and to maintain the desired concentration at the site of interest. Microspheres received much attention not only for prolonged release, but also for targeting of anti-diabetic drugs. Bilayer tablet via microsphere is new era for the successful development of controlled release formulation along with various features to provide a way of successful drug delivery system. Especially when in addition high production output is required. An attempt has been made in this review article to introduce the society to the current technological developments in bilayer and floating drug delivery system.

  3. Nanostructured antireflective bilayers: Optical design and preparation

    Energy Technology Data Exchange (ETDEWEB)

    Detrich, Ádám [Budapest University of Technology and Economics, Department of Physical Chemistry and Materials Science, Centre for Colloid Chemistry, H-1521 Budapest (Hungary); Nagy, Norbert [Research Centre for Natural Sciences (MTA TTK), Institute for Technical Physics and Materials Science (MFA), P.O. Box 49, H-1525 Budapest (Hungary); Nyári, Mária; Albert, Emőke; Zámbó, Dániel [Budapest University of Technology and Economics, Department of Physical Chemistry and Materials Science, Centre for Colloid Chemistry, H-1521 Budapest (Hungary); Hórvölgyi, Zoltán, E-mail: zhorvolgyi@mail.bme.hu [Budapest University of Technology and Economics, Department of Physical Chemistry and Materials Science, Centre for Colloid Chemistry, H-1521 Budapest (Hungary)

    2014-05-01

    We show different methods for tailoring and fabrication of various cost-effective antireflective nanocoatings on transparent and non-transparent substrates. The main purpose was to prepare coatings with decreased reflectance in the full visible wavelength range using simple wet layer deposition techniques. Structure of coatings was designed by optical simulations applying simplified calculations. The refractive index of substrates was also considered for the calculations. The advantageous optical properties were achieved by bilayered structures combining compact and porous sol–gel derived oxide layers and nanoparticulate films. The bilayered structures enhance the flexibility of design by not only the selection of the layer thicknesses but also by different ways of adjusting the effective refractive index of the layers. Furthermore, chemical stability of the coatings was also investigated. The optical and structural properties of prepared films and bilayered coatings were studied by UV–vis spectroscopy and scanning electron microscopy, respectively. The transmittance of coated glass substrates was above 97.5%, while the reflectance of coated silicon substrates was below 4% between 450 nm and 900 nm. - Highlights: • Designed antireflective bilayered coatings on glass and silicon. • Simple, colloid chemical approaches to preparation. • Favorable optical properties by combining compact and porous oxide layers. • Different ways for adjusting the effective refractive index. • Strong chemical resistance against acidic effects.

  4. Confinement of charge carriers in bilayer graphene

    NARCIS (Netherlands)

    Goossens, A.M.

    2013-01-01

    In this thesis we investigate the fundamental properties of electronic transport in bilayer graphene. We do this by confining electrons to narrow constrictions and small islands. Our key result is the fabrication and measurement of nanoscale devices that permit confinement with electric fields in b

  5. Confinement of charge carriers in bilayer graphene

    NARCIS (Netherlands)

    Goossens, A.M.

    2013-01-01

    In this thesis we investigate the fundamental properties of electronic transport in bilayer graphene. We do this by confining electrons to narrow constrictions and small islands. Our key result is the fabrication and measurement of nanoscale devices that permit confinement with electric fields in b

  6. Quantum pumping in a ballistic graphene bilayer

    NARCIS (Netherlands)

    Wakker, G.M.M.; Blaauboer, M.

    2010-01-01

    We investigate quantum pumping of massless Dirac fermions in an ideal (impurity free) double layer of graphene. The pumped current is generated by adiabatic variation in two gate voltages in the contact regions to a weakly doped double graphene sheet. At the Dirac point and for a wide bilayer with

  7. Bright Ion Channels and Lipid Bilayers

    NARCIS (Netherlands)

    Szymanski, Wiktor; Yilmaz, Duygu; Kocer, Armagan; Feringa, Ben L.

    2013-01-01

    If we look at a simple organism such as a zebrafish under a microscope, we would see many cells working in harmony. If we zoomed in, we would observe each unit performing its own tasks in a special aqueous environment isolated from the other units by a lipid bilayer approximately 5 nm thick. These

  8. Bifurcation of self-folded polygonal bilayers

    Science.gov (United States)

    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.

  9. Topological transformation of a surfactant bilayer

    DEFF Research Database (Denmark)

    Le, T.D.; Olsson, U.; Mortensen, K.

    2000-01-01

    Surfactant lamellar phases are often complicated by the formation of multilamellar (onions) under shear, which can originate simply by shaking the sample. A systematic study has been performed on the C10E3-D2O system in which different bilayer structures under a steady shear flow were investigated...

  10. Multiscale Modeling of Supported Lipid Bilayers

    Science.gov (United States)

    Hoopes, Matthew I.; Xing, Chenyue; Faller, Roland

    Cell membranes consist of a multitude of lipid molecules that serve as a framework for the even greater variety of membrane associated proteins [1-4]. As this highly complex (nonequilibrium) system cannot easily be understood and studied in a controlled way, a wide variety of model systems have been devised to understand the dynamics, structure, and thermodynamics in biological membranes. One such model system is a supported lipid bilayer (SLB), a two-dimensional membrane suspended on a surface. SLBs have been realized to be manageable experimentally while reproducing many of the key features of real biological membranes [5,6]. One of the main advantages of supported bilayers is the physical stability due to the solid support that enables a wide range of surface characterization techniques not available to free or unsupported membranes. As SLBs maintain some of the crucial structural and dynamic properties of biological membranes, they provide an important bridge to natural systems. In order to mimic cell membranes reliably, certain structural and dynamic features have to be reliably reproduced in the artificially constructed lipid bilayers. SLBs should display lateral mobility as in living cells, because many membrane activities involve transport, recruitment, or assembly of specific components. It is also critical for membranes to exhibit the correct thermodynamic phase, namely, a fluid lipid bilayer, to respond to environmental stress such as temperature and pressure changes [7]. There are several ways to fabricate supported lipid bilayers (SLBs) on planar substrates. One can use vesicle fusion on solid substrates [5,8-10] as well as Langmuir-Blodgett deposition [11,12]. Proteoliposome adsorption and subsequent membrane formation on a mica surface was first demonstrated by Brian and McConnell [13]. Because of its simplicity and reproducibility, this is one of the most common approaches to prepare supported membranes. A diverse range of different solid substrates

  11. Stokesian jellyfish: Viscous locomotion of bilayer vesicles

    CERN Document Server

    Evans, Arthur A; Lauga, Eric

    2010-01-01

    Motivated by recent advances in vesicle engineering, we consider theoretically the locomotion of shape-changing bilayer vesicles at low Reynolds number. By modulating their volume and membrane composition, the vesicles can be made to change shape quasi-statically in thermal equilibrium. When the control parameters are tuned appropriately to yield periodic shape changes which are not time-reversible, the result is a net swimming motion over one cycle of shape deformation. For two classical vesicle models (spontaneous curvature and bilayer coupling), we determine numerically the sequence of vesicle shapes through an enthalpy minimization, as well as the fluid-body interactions by solving a boundary integral formulation of the Stokes equations. For both models, net locomotion can be obtained either by continuously modulating fore-aft asymmetric vesicle shapes, or by crossing a continuous shape-transition region and alternating between fore-aft asymmetric and fore-aft symmetric shapes. The obtained hydrodynamic e...

  12. Electric Octupole Order in Bilayer Rashba System

    Science.gov (United States)

    Hitomi, Takanori; Yanase, Youichi

    2016-12-01

    The odd-parity multipole is an emergent degree of freedom, leading to spontaneous inversion symmetry breaking. The odd-parity multipole order may occur by forming staggered even-parity multipoles in a unit cell. We focus on a locally noncentrosymmetric bilayer Rashba system, and study an odd-parity electric octupole order caused by the antiferro stacking of local electric quadrupoles. Analyzing the forward scattering model, we show that the electric octupole order is stabilized by a layer-dependent Rashba spin-orbit coupling. The roles of the spin-orbit coupling are clarified on the basis of the analytic formula of multipole susceptibility. The spin texture allowed in the D2d point group symmetry and its magnetic response are revealed. Furthermore, we show that the parity-breaking quantum critical point appears in the magnetic field. The possible realization of the electric octupole order in bilayer high-Tc cuprate superconductors is discussed.

  13. Blood clotting reactions on nanoscale phospholipid bilayers.

    Science.gov (United States)

    Morrissey, James H; Pureza, Vincent; Davis-Harrison, Rebecca L; Sligar, Stephen G; Ohkubo, Y Zenmei; Tajkhorshid, Emad

    2008-01-01

    Blood clotting reactions, such as those catalyzed by the tissue factor:factor VIIa complex (TF:FVIIa), assemble on membrane surfaces containing anionic phospholipids such as phosphatidylserine (PS). In fact, membrane binding is critical for the function of most of the steps in the blood clotting cascade. In spite of this, our understanding of how the membrane contributes to catalysis, or even how these proteins interact with phospholipids, is incomplete. Making matters more complicated, membranes containing mixtures of PS and neutral phospholipids are known to spontaneously form PS-rich membrane microdomains in the presence of plasma concentrations of calcium ions, and it is likely that blood-clotting proteases such as TF:FVIIa partition into these PS-rich microdomains. Unfortunately, little is known about how membrane microdomain composition influences the activity of blood-clotting proteases, which is typically not under experimental control even in "simple" model membranes. Our laboratories have developed and applied new technologies for studying membrane proteins to gain insights into how blood-clotting protease-cofactor pairs assemble and function on membrane surfaces. This includes using a novel, nanoscale bilayer system (Nanodiscs) that permits assembling blood-clotting protease-cofactor pairs on stable bilayers containing from 65 to 250 phospholipid molecules per leaflet. We have used this system to investigate how local (nanometer-scale) changes in phospholipid bilayer composition modulate TF:FVIIa activity. We have also used detailed molecular-dynamics simulations of nanoscale bilayers to provide atomic-scale predictions of how the membrane-binding domain of factor VIIa interacts with PS in membranes.

  14. Self-folding graphene-polymer bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Tao [Institute of Microelectronics, Tsinghua University, Beijing 100084 (China); Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Yoon, ChangKyu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Jin, Qianru [Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Li, Mingen [Department of Physics, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Liu, Zewen [Institute of Microelectronics, Tsinghua University, Beijing 100084 (China); Gracias, David H., E-mail: dgracias@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Department of Chemical and Biomolecular Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States)

    2015-05-18

    In order to incorporate the extraordinary intrinsic thermal, electrical, mechanical, and optical properties of graphene with three dimensional (3D) flexible substrates, we introduce a solvent-driven self-folding approach using graphene-polymer bilayers. A polymer (SU-8) film was spin coated atop chemically vapor deposited graphene films on wafer substrates and graphene-polymer bilayers were patterned with or without metal electrodes using photolithography, thin film deposition, and etching. After patterning, the bilayers were released from the substrates and they self-folded to form fully integrated, curved, and folded structures. In contrast to planar graphene sensors on rigid substrates, we assembled curved and folded sensors that are flexible and they feature smaller form factors due to their 3D geometry and large surface areas due to their multiple rolled architectures. We believe that this approach could be used to assemble a range of high performance 3D electronic and optical devices of relevance to sensing, diagnostics, wearables, and energy harvesting.

  15. Self-folding graphene-polymer bilayers

    Science.gov (United States)

    Deng, Tao; Yoon, ChangKyu; Jin, Qianru; Li, Mingen; Liu, Zewen; Gracias, David H.

    2015-05-01

    In order to incorporate the extraordinary intrinsic thermal, electrical, mechanical, and optical properties of graphene with three dimensional (3D) flexible substrates, we introduce a solvent-driven self-folding approach using graphene-polymer bilayers. A polymer (SU-8) film was spin coated atop chemically vapor deposited graphene films on wafer substrates and graphene-polymer bilayers were patterned with or without metal electrodes using photolithography, thin film deposition, and etching. After patterning, the bilayers were released from the substrates and they self-folded to form fully integrated, curved, and folded structures. In contrast to planar graphene sensors on rigid substrates, we assembled curved and folded sensors that are flexible and they feature smaller form factors due to their 3D geometry and large surface areas due to their multiple rolled architectures. We believe that this approach could be used to assemble a range of high performance 3D electronic and optical devices of relevance to sensing, diagnostics, wearables, and energy harvesting.

  16. Structure of twisted and buckled bilayer graphene

    Science.gov (United States)

    Jain, Sandeep K.; Juričić, Vladimir; Barkema, Gerard T.

    2017-03-01

    We study the atomic structure of twisted bilayer graphene, with very small mismatch angles (θ ∼ {0.28}0), a topic of intense recent interest. We use simulations, in which we combine a recently presented semi-empirical potential for single-layer graphene, with a new term for out-of-plane deformations, (Jain et al 2015 J. Phys. Chem. C 119 9646) and an often-used interlayer potential (Kolmogorov et al 2005 Phys. Rev. B 71 235415). This combination of potentials is computationally cheap but accurate and precise at the same time, allowing us to study very large samples, which is necessary to reach very small mismatch angles in periodic samples. By performing large scale atomistic simulations, we show that the vortices appearing in the Moiré pattern in the twisted bilayer graphene samples converge to a constant size in the thermodynamic limit. Furthermore, the well known sinusoidal behavior of energy no longer persists once the misorientation angle becomes very small (θ \\lt {1}0). We also show that there is a significant buckling after the relaxation in the samples, with the buckling height proportional to the system size. These structural properties have direct consequences on the electronic and optical properties of bilayer graphene.

  17. Ion beam mixing isotopic metal bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Fell, C.J. [Newcastle Univ., NSW (Australia). Dept. of Physics; Kenny, M.J. [CSIRO, Lindfield, NSW (Australia). Div. of Applied Physics

    1993-12-31

    In order to obtain an insight into the mechanisms of ion-solid interactions, bilayer targets can be prepared from two different isotopes. A mixing study SIMS is to be carried out using specially grown monocrystalline bilayers of {sup 58}Ni / {sup 60}Ni. An important aspect of the work is the preparation of high quality single-crystal thin films. The Ni layers will be grown on the (110) surface of pure Ni and verified for crystallinity using Reflection High-Energy Electron Diffraction and Rutherford Backscattering channelling analysis. The Pd bilayers will be grown on a Pd (100) surface. RHEED will be used to confirm the two-dimensional crystallinity of the surface before and after deposition of each layer, and channelling used to confirm bulk film crystallinity. Single crystal substrates are currently being prepared. Analysis of the Ni (110) surface using RHEED at 9 kV shows a streak spacing which corresponds to a lattice spacing of 2.47 {+-} 0.09 Angstroms. 9 refs., 1 fig.

  18. Molecular dynamics modelling of EGCG clusters on ceramide bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Yeo, Jingjie; Cheng, Yuan; Li, Weifeng; Zhang, Yong-Wei [Institute of High Performance Computing, A*STAR, 138632 (Singapore)

    2015-12-31

    A novel method of atomistic modelling and characterization of both pure ceramide and mixed lipid bilayers is being developed, using only the General Amber ForceField. Lipid bilayers modelled as pure ceramides adopt hexagonal packing after equilibration, and the area per lipid and bilayer thickness are consistent with previously reported theoretical results. Mixed lipid bilayers are modelled as a combination of ceramides, cholesterol, and free fatty acids. This model is shown to be stable after equilibration. Green tea extract, also known as epigallocatechin-3-gallate, is introduced as a spherical cluster on the surface of the mixed lipid bilayer. It is demonstrated that the cluster is able to bind to the bilayers as a cluster without diffusing into the surrounding water.

  19. Method of fabricating lipid bilayer membranes on solid supports

    Science.gov (United States)

    Cho, Nam-Joon (Inventor); Frank, Curtis W. (Inventor); Glenn, Jeffrey S. (Inventor); Cheong, Kwang Ho (Inventor)

    2012-01-01

    The present invention provides a method of producing a planar lipid bilayer on a solid support. With this method, a solution of lipid vesicles is first deposited on the solid support. Next, the lipid vesicles are destabilized by adding an amphipathic peptide solution to the lipid vesicle solution. This destabilization leads to production of a planar lipid bilayer on the solid support. The present invention also provides a supported planar lipid bilayer, where the planar lipid bilayer is made of naturally occurring lipids and the solid support is made of unmodified gold or titanium oxide. Preferably, the supported planar lipid bilayer is continuous. The planar lipid bilayer may be made of any naturally occurring lipid or mixture of lipids, including, but not limited to phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylinsitol, cardiolipin, cholesterol, and sphingomyelin.

  20. Equilibrium insertion of nanoscale objects into phospholipid bilayers

    CERN Document Server

    Pogodin, Sergey

    2011-01-01

    Certain membrane proteins, peptides, nanoparticles and nanotubes have rigid structure and fixed shape. They are often viewed as spheres and cylinders with certain surface properties. Single Chain Mean Field theory is used to model the equilibrium insertion of nanoscale spheres and rods into the phospholipid bilayer. The equilibrium structures and the resulting free energies of the nano-objects in the bilayer allow to distinguish different orientations in the bilayer and estimate the energy barrier of insertion.

  1. Multiple locations of peptides in the hydrocarbon core of gel-phase membranes revealed by peptide (13)C to lipid (2)H rotational-echo double-resonance solid-state nuclear magnetic resonance.

    Science.gov (United States)

    Xie, Li; Jia, Lihui; Liang, Shuang; Weliky, David P

    2015-01-27

    Membrane locations of peptides and proteins are often critical to their functions. Solid-state rotational-echo double-resonance (REDOR) nuclear magnetic resonance is applied to probe the locations of two peptides via peptide (13)CO to lipid (2)H distance measurements. The peptides are KALP, an α-helical membrane-spanning peptide, and HFP, the β-sheet N-terminal fusion peptide of the HIV gp41 fusion protein that plays an important role in HIV-host cell membrane fusion. Both peptides are shown to have at least two distinct locations within the hydrocarbon core of gel-phase membranes. The multiple locations are attributed to snorkeling of lysine side chains for KALP and to the distribution of antiparallel β-sheet registries for HFP. The relative population of each location is also quantitated. To the best of our knowledge, this is the first clear experimental support of multiple peptide locations within the membrane hydrocarbon core. These data are for gel-phase membranes, but the approach should work for liquid-ordered membranes containing cholesterol and may be applicable to liquid-disordered membranes with appropriate additional analysis to take into account protein and lipid motion. This paper also describes the methodological development of (13)CO-(2)H REDOR using the lyophilized I4 peptide that is α-helical and (13)CO-labeled at A9 and (2)Hα-labeled at A8. The I4 spins are well-approximated as an ensemble of isolated (13)CO-(2)H spin pairs each separated by 5.0 Å with a 37 Hz dipolar coupling. A pulse sequence with rectangular 100 kHz (2)H π pulses results in rapid and extensive buildup of REDOR (ΔS/S0) with a dephasing time (τ). The buildup is well-fit by a simple exponential function with a rate of 24 Hz and an extent close to 1. These parameter values reflect nonradiative transitions between the (2)H spin states during the dephasing period. Each spin pair spends approximately two-thirds of its time in the (13)CO-(2)H (m = ±1) states and

  2. Intercalation of small hydrophobic molecules in lipid bilayers containing cholesterol

    Energy Technology Data Exchange (ETDEWEB)

    Worcester, D.L.; Hamacher, K.; Kaiser, H.; Kulasekere, R.; Torbet, J. [Univ. of Missouri, Columbia, MO (United States)

    1994-12-31

    Partitioning of small hydrophobic molecules into lipid bilayers containing cholesterol has been studied using the 2XC diffractometer at the University of Missouri Research Reactor. Locations of the compounds were determined by Fourier difference methods with data from both deuterated and undeuterated compounds introduced into the bilayers from the vapor phase. Data fitting procedures were developed for determining how well the compounds were localized. The compounds were found to be localized in a narrow region at the center of the hydrophobic layer, between the two halves of the bilayer. The structures are therefore intercalated structures with the long axis of the molecules in the plane of the bilayer.

  3. Pair interaction of bilayer-coated nanoscopic particles

    Institute of Scientific and Technical Information of China (English)

    Zhang Qi-Yi

    2009-01-01

    The pair interaction between bilayer membrane-coated nanosized particles has been explored by using the self-consistent field (SCF) theory. The bilayer membranes are composed of amphiphilic polymers. For different system parameters, the pair-interaction free energies are obtained. Particular emphasis is placcd on the analysis of a sequence of structural transformations of bilayers on spherical particles, which occur during their approaching processes. For different head fractions of amphiphilcs, the asymmetrical morphologies between bilayers on two particles and the inverted micellar intermediates have been found in the membrane fusion pathway. These results can benefit the fabrication of vesicles as encapsulation vectors for drug and gene delivery.

  4. Faraday rotation in bilayer graphene-based integrated microcavity.

    Science.gov (United States)

    Da, Hai-Xia; Yan, Xiao-Hong

    2016-01-01

    Bernal-stacked bilayer graphene has rich ground states with various broken symmetries, allowing the existence of magneto-optical (MO) effects even in the absence of an external magnetic field. Here we report controllable Faraday rotation (FR) of bilayer graphene induced by electrostatic gate voltage, whose value is 10 times smaller than the case of single layer graphene with a magnetic field. A proposed bilayer graphene-based microcavity configuration enables the enhanced FR angle due to the large localized electromagnetic field. Our results offer unique opportunities to apply bilayer graphene for MO devices.

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

    Science.gov (United States)

    Taylor, Graham J; Venkatesan, Guru A; Collier, C Patrick; Sarles, Stephen A

    2015-10-14

    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 for 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.

  6. Bilayer-thickness-mediated interactions between integral membrane proteins.

    Science.gov (United States)

    Kahraman, Osman; Koch, Peter D; Klug, William S; Haselwandter, Christoph A

    2016-04-01

    Hydrophobic thickness mismatch between integral membrane proteins and the surrounding lipid bilayer can produce lipid bilayer thickness deformations. Experiment and theory have shown that protein-induced lipid bilayer thickness deformations can yield energetically favorable bilayer-mediated interactions between integral membrane proteins, and large-scale organization of integral membrane proteins into protein clusters in cell membranes. Within the continuum elasticity theory of membranes, the energy cost of protein-induced bilayer thickness deformations can be captured by considering compression and expansion of the bilayer hydrophobic core, membrane tension, and bilayer bending, resulting in biharmonic equilibrium equations describing the shape of lipid bilayers for a given set of bilayer-protein boundary conditions. Here we develop a combined analytic and numerical methodology for the solution of the equilibrium elastic equations associated with protein-induced lipid bilayer deformations. Our methodology allows accurate prediction of thickness-mediated protein interactions for arbitrary protein symmetries at arbitrary protein separations and relative orientations. We provide exact analytic solutions for cylindrical integral membrane proteins with constant and varying hydrophobic thickness, and develop perturbative analytic solutions for noncylindrical protein shapes. We complement these analytic solutions, and assess their accuracy, by developing both finite element and finite difference numerical solution schemes. We provide error estimates of our numerical solution schemes and systematically assess their convergence properties. Taken together, the work presented here puts into place an analytic and numerical framework which allows calculation of bilayer-mediated elastic interactions between integral membrane proteins for the complicated protein shapes suggested by structural biology and at the small protein separations most relevant for the crowded membrane

  7. Giant magnetoresistance in bilayer graphene nanoflakes

    Science.gov (United States)

    Farghadan, Rouhollah; Farekiyan, Marzieh

    2016-09-01

    Coherent spin transport through bilayer graphene (BLG) nanoflakes sandwiched between two electrodes made of single-layer zigzag graphene nanoribbon was investigated by means of Landauer-Buttiker formalism. Application of a magnetic field only on BLG structure as a channel produces a perfect spin polarization in a large energy region. Moreover, the conductance could be strongly modulated by magnetization of the zigzag edge of AB-stacked BLG, and the junction, entirely made of carbon, produces a giant magnetoresistance (GMR) up to 100%. Intestinally, GMR and spin polarization could be tuned by varying BLG width and length. Generally, MR in a AB-stacked BLG strongly increases (decreases) with length (width).

  8. Twisted CFT and bilayer Quantum Hall systems

    CERN Document Server

    Cristofano, G; Naddeo, A

    2003-01-01

    We identify the impurity interactions of the recently proposed CFT description of a bilayer Quantum Hall system at filling nu =m/(pm+2) in Mod. Phys. Lett. A 15 (2000) 1679. Such a CFT is obtained by m-reduction on the one layer system, with a resulting pairing symmetry and presence of quasi-holes. For the m=2 case boundary terms are shown to describe an impurity interaction which allows for a localized tunnel of the Kondo problem type. The presence of an anomalous fixed point is evidenced at finite coupling which is unstable with respect to unbalance and flows to a vacuum state with no quasi-holes.

  9. Vortex dynamics in ferromagnetic/superconducting bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Cieplak, M.Z.; Adamus, Z. [Polish Acad Sci, Inst Phys, PL-02668 Warsaw, (Poland); Konczykowski, M. [CEA, DSM, DRECAM, Lab Solides Irradies, Ecole Polytechnique, CNRS-UMR 7642, F-91128 Palaiseau (France); Zhu, L.Y.; Chien, C.L. [Johns Hopkins Univ, Dept Phys and Astron, Baltimore, MD 21218 (United States)

    2008-07-01

    The dependence of vortex dynamics on the geometry of magnetic domain pattern is studied in the superconducting/ferromagnetic bilayers, in which niobium is a superconductor, and Co/Pt multilayer with perpendicular magnetic anisotropy serves as a ferromagnetic layer. Magnetic domain patterns with different density of domains per surface area and different domain size, w, are obtained for Co/Pt with different thickness of Pt. The dense patterns of domains with the size comparable to the magnetic penetration depth (w {>=} {lambda}) produce large vortex pinning and smooth vortex penetration, while less dense patterns with larger domains (w {>=}{>=} {lambda}) enhance pinning less effectively and result in flux jumps during flux motion. (authors)

  10. Interaction of neurotransmitters with a phospholipid bilayer

    DEFF Research Database (Denmark)

    Peters, Günther H.J.; Werge, Mikkel; Elf-Lind, Maria Northved

    2014-01-01

    We have performed a series of molecular dynamics simulations to study the interactions between the neurotransmitters (NTs) γ-aminobutyrate (GABA), glycine (GLY), acetylcholine (ACH) and glutamate (GLU) as well as the amidated/acetylated γ-aminobutyrate (GABAneu) and the osmolyte molecule glycerol...... umbrella sampling simulations, which were conducted for the four naturally occurring NTs. Free energy profiles for ACH and GLU show a minimum of ∼2–3 kJ/mol close to the bilayer interface, while for GABA and GLY, a minimum of respectively ∼2 kJ/mol and ∼5 kJ/mol is observed when these NTs are located...

  11. Bilayer avalanche spin-diode logic

    Energy Technology Data Exchange (ETDEWEB)

    Friedman, Joseph S., E-mail: joseph.friedman@u-psud.fr; Querlioz, Damien [Institut d’Electronique Fondamentale, Univ. Paris-Sud, CNRS, 91405 Orsay (France); Fadel, Eric R. [Department of Materials Science, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Wessels, Bruce W. [Department of Electrical Engineering & Computer Science, Northwestern University, Evanston, IL 60208 (United States); Department of Materials Science & Engineering, Northwestern University, Evanston, IL 60208 (United States); Sahakian, Alan V. [Department of Electrical Engineering & Computer Science, Northwestern University, Evanston, IL 60208 (United States); Department of Biomedical Engineering, Northwestern University, Evanston, IL 60208 (United States)

    2015-11-15

    A novel spintronic computing paradigm is proposed and analyzed in which InSb p-n bilayer avalanche spin-diodes are cascaded to efficiently perform complex logic operations. This spin-diode logic family uses control wires to generate magnetic fields that modulate the resistance of the spin-diodes, and currents through these devices control the resistance of cascaded devices. Electromagnetic simulations are performed to demonstrate the cascading mechanism, and guidelines are provided for the development of this innovative computing technology. This cascading scheme permits compact logic circuits with switching speeds determined by electromagnetic wave propagation rather than electron motion, enabling high-performance spintronic computing.

  12. Rich Polymorphic Behavior of Wigner Bilayers

    Science.gov (United States)

    Antlanger, Moritz; Kahl, Gerhard; Mazars, Martial; Šamaj, Ladislav; Trizac, Emmanuel

    2016-09-01

    Self-assembly into target structures is an efficient material design strategy. Combining analytical calculations and computational techniques of evolutionary and Monte Carlo types, we report about a remarkable structural variability of Wigner bilayer ground states, when charges are confined between parallel charged plates. Changing the interlayer separation, or the plate charge asymmetry, a cascade of ordered patterns emerges. At variance with the symmetric case phenomenology, the competition between commensurability features and charge neutralization leads to long range attraction, appearance of macroscopic charges, exotic phases, and nonconventional phase transitions with distinct critical indices, offering the possibility of a subtle, but precise and convenient control over patterns.

  13. Cholesterol orientation and tilt modulus in DMPC bilayers

    OpenAIRE

    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...

  14. Effect of Undulations on Surface Tension in Simulated Bilayers

    NARCIS (Netherlands)

    Marrink, S.J.; Mark, A.E.

    2001-01-01

    To understand the effect of the finite size of simulation cells on the equilibrium properties of bilayers, an extensive series of glycerolmonoolein bilayer molecular dynamics simulations in which the surface area and system size were systematically changed have been conducted. Systems ranging from

  15. Fluid lipid bilayers: Intermonolayer coupling and its thermodynamic manifestations

    DEFF Research Database (Denmark)

    Hansen, Per Lyngs; Miao, Ling; Ipsen, John Hjorth

    1998-01-01

    A fluid membrane of lipid bilayer consists of two individual molecular monolayers physically opposed to each other. This unique molecular architecture naturally necessitates the need to treat a lipid-bilayer membrane as one entity of two coupled two-dimensional systems (monolayers), each of which...

  16. Alpha-tocopherol inhibits pore formation in the oxidized bilayers

    CERN Document Server

    Boonnoy, Phansiri; Wong-ekkabut, Jirasak

    2016-01-01

    In biological membranes, alpha-tocopherols ({\\alpha}-toc; vitamin E) protect polyunsaturated lipids from free radicals. Although the interactions of {\\alpha}-toc with non-oxidized lipid bilayers have been studied, their on oxidized bilayers remain unknown. In this study, atomistic molecular dynamics (MD) simulations of oxidized lipid bilayers were performed with varying concentrations of {\\alpha}-toc. Bilayers with 1-palmitoyl-2-lauroyl-sn-glycero-3-phosphocholine (PLPC) lipids and its aldehyde derivatives at 1:1 ratio were studied. Our simulations show that oxidized lipids self-assemble into aggregates with a water pore rapidly developing across the lipid bilayer. The free energy of transporting an {\\alpha}-toc molecule in a lipid bilayer suggests that {\\alpha}-tocs can passively adsorb into the bilayer. When {\\alpha}-toc molecules were present at low concentrations in bilayers containing oxidized lipids, the formation of water pores was slowed down. At high {\\alpha}-toc concentra-tions, no pores were observ...

  17. Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

    Science.gov (United States)

    Schrader, Alex M.; Cheng, Chi-Yuan; Israelachvili, Jacob N.; Han, Songi

    2016-07-01

    Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relative to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity.

  18. Regulation of sodium channel function by bilayer elasticity

    DEFF Research Database (Denmark)

    Lundbaek, Jens A; Birn, Pia; Hansen, Anker J

    2004-01-01

    be a general mechanism regulating membrane protein function, we examined whether voltage-dependent skeletal-muscle sodium channels, expressed in HEK293 cells, are regulated by bilayer elasticity, as monitored using gramicidin A (gA) channels. Nonphysiological amphiphiles (beta-octyl-glucoside, Genapol X-100......, Triton X-100, and reduced Triton X-100) that make lipid bilayers less "stiff", as measured using gA channels, shift the voltage dependence of sodium channel inactivation toward more hyperpolarized potentials. At low amphiphile concentration, the magnitude of the shift is linearly correlated to the change...... in gA channel lifetime. Cholesterol-depletion, which also reduces bilayer stiffness, causes a similar shift in sodium channel inactivation. These results provide strong support for the notion that bilayer-protein hydrophobic coupling allows the bilayer elastic properties to regulate membrane protein...

  19. Engineering Lipid Bilayer Membranes for Protein Studies

    Directory of Open Access Journals (Sweden)

    Muhammad Shuja Khan

    2013-10-01

    Full Text Available Lipid membranes regulate the flow of nutrients and communication signaling between cells and protect the sub-cellular structures. Recent attempts to fabricate artificial systems using nanostructures that mimic the physiological properties of natural lipid bilayer membranes (LBM fused with transmembrane proteins have helped demonstrate the importance of temperature, pH, ionic strength, adsorption behavior, conformational reorientation and surface density in cellular membranes which all affect the incorporation of proteins on solid surfaces. Much of this work is performed on artificial templates made of polymer sponges or porous materials based on alumina, mica, and porous silicon (PSi surfaces. For example, porous silicon materials have high biocompatibility, biodegradability, and photoluminescence, which allow them to be used both as a support structure for lipid bilayers or a template to measure the electrochemical functionality of living cells grown over the surface as in vivo. The variety of these media, coupled with the complex physiological conditions present in living systems, warrant a summary and prospectus detailing which artificial systems provide the most promise for different biological conditions. This study summarizes the use of electrochemical impedance spectroscopy (EIS data on artificial biological membranes that are closely matched with previously published biological systems using both black lipid membrane and patch clamp techniques.

  20. Reversible Polarization Rotation in Epitaxial Ferroelectric Bilayers

    DEFF Research Database (Denmark)

    Liu, Guangqing; Zhang, Qi; Huang, Hsin-Hui

    2016-01-01

    Polarization rotation engineering is a promising path to giant dielectric and electromechanical responses in ferroelectric materials and devices. This work demonstrates robust and reversible in- to out-of-plane polarization rotation in ultrathin (nanoscale) epitaxial (001) tetragonal PbZr0.3Ti0.7O3...... (PZT-T)/rhombohedral PbZr0.55Ti0.45O3 (PZT-R) ferroelectric bilayers. An underlying 20 nm thick PZT-R layer reduces the symmetry in a 5 nm thick PZT-T layer by imposing an in-plane tensile strain while simultaneously decoupling the PZT-T layer from the substrate. This prevents clamping and facilitates...... large-scale polarization rotation switching (≈60 μC cm−2) and an effective d 33 response 500% (≈250 pm V−1) larger than the PZT-R layer alone. Furthermore, this enhancement is stable for more than 107 electrical switching cycles. These bilayers present a simple and highly controllable means to design...

  1. Theoretical study on stability of hybrid bilayers

    Science.gov (United States)

    Silva, Thiago S.; de Lima Bernardo, Bertúlio; Azevedo, Sèrgio

    2015-04-01

    Motivated by the recent experimental realization of the hybrid nanostructure of graphene and boron nitride (h-BN) sheet, and studies of gap modulation by strain, we use first principles calculations based on density functional theory to investigate the effects of strain in hybrid bilayers composed of two monolayers of graphene with a nanodomain of {{B}3}{{N}3}. The calculations were made with two different approximations for the functional exchange-correlation, GGA and VDW-DF. We investigate the modification in the electronic structure and structural properties of various configurations of the hybrid bilayers. Among the configurations, those with Bernal stacking are found to be more stable when compared to the others. Studies of the compressive strain influence were made only in the structure that has been shown to be the most stable. We have found that the two approximations used in the calculations exhibit the same results for the electronic properties of all structures. The opening of the energy gap due to strain was possible in the calculations by using the GGA approximation, but the same does not happen in the calculations using the VDW-DF approximation. Our analysis shows that the VDW-DF approximation is better suited for studies involving surfaces.

  2. On distance variation effects on graphene bilayers

    Science.gov (United States)

    Naji, S.; Bhihi, M.; Labrim, H.; Belhaj, A.; Benyoussef, A.; El Kenz, A.; Loulidi, M.

    2014-06-01

    The opening of the energy gap and the total energy of the graphene-like bilayers are investigated using ab initio calculations. The studied model consists of a static single layer of graphene interacting with an extra dynamic one placed at a varying vertical distance d in the (AB) stacking arrangement. The effects of the vertical distance variation on the energy gap and the total energy of the system are discussed first. Starting from a distance around the van der Waals length, the energy gap does not depend on the vertical distance variation and the system exhibits graphene-like properties with minor deformations in the lattice size parameter and the energy dispersion behaviour around K points. However, it has been shown that the diagonal distance variation of the graphene-like bilayer modifies the electronic structure properties. This modification depends on an intermediate stacking arrangement between the (AA) and the (AB) configurations. It has been shown that the diagonal distance variation has an influence on the states of pz electrons in the (AB) arrangement and it can be explored to open the energy gap.

  3. Measuring Interlayer Shear Stress in Bilayer Graphene

    Science.gov (United States)

    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.

  4. Theory of skyrmions in bilayer systems

    Science.gov (United States)

    Koshibae, Wataru; Nagaosa, Naoto

    2017-02-01

    Skyrmion is an emergent particle consisting of many spins in magnets, and has many nontrivial features such as (i) nano-scale size, (ii) topological stability, (iii) gyrodynamics, and (iv) highly efficient spin transfer torque, which make skyrmions the promising candidate for the magnetic devices. Earlier works were focusing on the bulk or thin film of Dzyaloshinskii-Moriya (DM) magnets, while recent advances are focusing on the skyrmions induced by the interfaces. Therefore, the superstructures naturally leads to the interacting skyrmions on different interfaces, which has unique dynamics compared with those on the same interface. Here we theoretically study the two skyrmions on bilayer systems employing micromagnetic simulations as well as the analysis based on Thiele equation, revealing the reaction between them such as the collision and bound state formation. The dynamics depends sensitively on the sign of DM interactions, i.e., helicities, and skyrmion numbers of two skyrmions, which can be well described by Thiele equation. Furthermore, we have found the colossal spin-transfer-torque effect of bound skyrmion pair on antiferromagnetically coupled bilayer systems.

  5. Mode of interaction of ganglioside Langmuir monolayer originated from echinoderms: three binary systems of ganglioside/DPPC, ganglioside/DMPE, and ganglioside/cholesterol.

    Science.gov (United States)

    Hoda, Kazuki; Ikeda, Yuriko; Kawasaki, Hideya; Yamada, Koji; Higuchi, Ryuichi; Shibata, Osamu

    2006-09-01

    The surface pressure (pi)-area (A), the surface potential (DeltaV)-A, and the dipole moment (mu( perpendicular))-A isotherms were obtained for monolayers made from a ganglioside originated from echinoderms [Diadema setosum ganglioside (DSG-1)], dipalmitoylphosphatidylcholine (DPPC), dimyristoylphosphatidylethanolamine (DMPE), cholesterol (Ch), and their combinations. Monolayers spread on several different substrates were investigated at the air/water interface by the Wilhelmy method, ionizing electrode method, fluorescence microscopy (FM) and atomic force microscopy (AFM). Surface potentials (DeltaV) of pure components were analyzed using the three-layer model proposed by Demchak and Fort [R.J. Demchak, T. Fort, J. Colloid Interface Sci. 46 (1974) 191-202]. The new finding was that DSG-1 was stable and showed a liquid-expanded film and that its monolayer behavior of DeltaV was sensitive for the change of the NaCl concentration in the subphase. Moreover, the miscibility of DSG-1 and three major lipids in the two-component monolayers was examined by plotting the variation of the molecular area and the surface potential as a function of the DSG-1 molar fraction (X(DSG-1)), using the additivity rule. From the A-X(DSG-1) and DeltaV(m)-X(DSG-1) plots, partial molecular surface area (PMA) and apparent partial molecular surface potential (APSP) were determined at the discrete surface pressure. The PMA and APSP with the mole fraction were extensively discussed for the miscible system. The miscibility was also investigated from the two-dimensional phase diagrams. Furthermore, a regular surface mixture, for which the Joos equation was used for the analysis of the collapse pressure of two-component monolayers, allowed calculation of the interaction parameter (xi) and the interaction energy (-Deltavarepsilon) between them. The observations using fluorescence microscopy and AFM image also provide us the miscibility in the monolayer state.

  6. Spin-labeled gramicidin a: channel formation and dissociation.

    Science.gov (United States)

    Dzikovski, Boris G; Borbat, Petr P; Freed, Jack H

    2004-11-01

    Gramicidin A was studied by continuous wave electron spin resonance (CW-ESR) and by double-quantum coherence electron spin resonance (DQC-ESR) in several lipid membranes (using samples that were macroscopically aligned by isopotential spin-dry ultracentrifugation) and vesicles. As a reporter group, the nitroxide spin-label was attached at the C-terminus yielding the spin-labeled product (GAsl). ESR spectra of aligned membranes containing GAsl show strong orientation dependence. In DPPC and DSPC membranes at room temperature the spectral shape is consistent with high ordering, which, in conjunction with the observed high polarity of the environment of the nitroxide, is interpreted in terms of the nitroxide moiety being close to the membrane surface. In contrast, spectra of GAsl in DMPC membranes indicate deeper embedding and tilt of the NO group. The GAsl spectrum in the DPPC membrane at 35 degrees C (the gel to Pbeta phase transition) exhibits sharp changes, and above this temperature becomes similar to that of DMPC. The dipolar spectrum from DQC-ESR clearly indicates the presence of pairs in DMPC membranes. This is not the case for DPPC, rapidly frozen from the gel phase; however, there are hints of aggregation. The interspin distance in the pairs is 30.9 A, in good agreement with estimates for the head-to-head GAsl dimer (the channel-forming conformation), which matches the hydrophobic thickness of the DMPC bilayer. Both DPPC and DSPC, apparently as a result of hydrophobic mismatch between the dimer length and bilayer thickness, do not favor the channel formation in the gel phase. In the Pbeta and Lalpha phases of DPPC (above 35 degrees C) the channel dimer forms, as evidenced by the DQC-ESR dipolar spectrum after rapid freezing. It is associated with a lateral expansion of lipid molecules and a concomitant decrease in bilayer thickness, which reduces the hydrophobic mismatch. A comparison with studies of dimer formation by other physical techniques indicates the

  7. Effects of Dimethyl Sulfoxide on Surface Water near Phospholipid Bilayers.

    Science.gov (United States)

    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 (XDMSO), 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 XDMSO(≲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.

  8. Experimental demonstration of a bilayer thermal cloak.

    Science.gov (United States)

    Han, Tiancheng; Bai, Xue; Gao, Dongliang; Thong, John T L; Li, Baowen; Qiu, Cheng-Wei

    2014-02-07

    Invisibility has attracted intensive research in various communities, e.g., optics, electromagnetics, acoustics, thermodynamics, dc, etc. However, many experimental demonstrations have only been achieved by virtue of simplified approaches due to the inhomogeneous and extreme parameters imposed by the transformation-optic method, and usually require a challenging realization with metamaterials. In this Letter, we demonstrate a bilayer thermal cloak made of bulk isotropic materials, and it has been validated as an exact cloak. We experimentally verified its ability to maintain the heat front and its heat protection capabilities in a 2D proof-of-concept experiment. The robustness of this scheme is validated in both 2D (including oblique heat front incidence) and 3D configurations. The proposed scheme may open a new avenue to control the diffusive heat flow in ways inconceivable with phonons, and also inspire new alternatives to the functionalities promised by transformation optics.

  9. Combinatorics of giant hexagonal bilayer hemoglobins.

    Science.gov (United States)

    Hanin, L G; Vinogradov, S N

    2000-01-01

    The paper discusses combinatorial and probabilistic models allowing to characterize various aspects of spacial symmetry and structural heterogeneity of the giant hexagonal bilayer hemoglobins (HBL Hb). Linker-dodecamer configurations of HBL are described for two and four linker types (occurring in the two most studied HBL Hb of Arenicola and Lumbricus, respectively), and the most probable configurations are found. It is shown that, for HBL with marked dodecamers, the number of 'normal-marked' pairs of dodecamers in homological position follows a binomial distribution. The group of symmetries of the dodecamer substructure of HBL is identified with the dihedral group D6. Under natural symmetry assumptions, the total dipole moment of the dodecamer substructure of HBL is shown to be zero. Biological implications of the mathematical findings are discussed.

  10. Space charge and screening in bilayer graphene

    Science.gov (United States)

    Kolomeisky, Eugene B.; Straley, Joseph P.; Abrams, Daniel L.

    2016-11-01

    Undoped bilayer graphene is a two-dimensional semimetal with a low-energy excitation spectrum that is parabolic in the momentum. As a result, the screening of an arbitrary external charge Ze is accompanied by a reconstruction of the ground state: valence band electrons (for Z  >  0) are promoted to form a space charge around the charge while the holes leave the physical picture. The outcome is a flat neutral object resembling the regular atom except that for Z\\gg 1 it is described by a strictly linear Thomas-Fermi theory. This theory also predicts that the bilayer’s static dielectric constant is the same as that of a two-dimensional electron gas in the long-wavelength limit.

  11. Oxygen diffusion in bilayer polymer films

    DEFF Research Database (Denmark)

    Poulsen, Lars; Zebger, Ingo; Tofte, Jannik Pentti;

    2004-01-01

    Experiments to quantify oxygen diffusion have been performed on polymer samples in which a film of poly(ethylene-co-norbornene) was cast onto a film of polystyrene which, in turn, was cast onto an oxygen-impermeable substrate. In the technique employed, the time evolution of oxygen transport...... through the film of poly(ethylene-co-norbornene) and into the polystyrene film was monitored using the phosphorescence of singlet oxygen as a spectroscopic probe. To analyze the data, it was necessary to solve Fick's second law of diffusion for both polymer films. Tractable analytical and numerical...... solutions were obtained for the problem. Moreover, the numerical solution is sufficiently general that it can be used to simulate oxygen concentration profiles in films consisting of more than two layers. Data obtained from the bilayer films yield a diffusion coefficient for oxygen in poly...

  12. The effects of globotriaosylceramide tail saturation level on bilayer phases

    DEFF Research Database (Denmark)

    Pezeshkian, Weria; Chaban, Vitaly V; Johannes, Ludger

    2015-01-01

    of the Gb3 concentration and its acyl chain saturation on the phase behaviour of a mixed bilayer of dioleoylphosphatidylcholine and Gb3. The simulation results show that: (1) the Gb3 acyl chains (longer tails) from one leaflet interdigitate into the opposing leaflet and lead to significant bilayer...... rigidification and immobilisation of the lipid tails. S-Gb3 can form a highly ordered, relatively immobile phase which is resistant to bending while these changes for U-Gb3 are not significant. (2) At low concentrations of Gb3, U-Gb3 and S-Gb3 have a similar impact on the bilayer reminiscent of the effect...

  13. Modeling liquid crystal bilayer structures with minimal surfaces.

    Science.gov (United States)

    Enlow, J D; Enlow, R L; McGrath, K M; Tate, M W

    2004-01-22

    This paper describes a new convenient and accurate method of calculating x-ray diffraction integrated intensities from detailed cubic bilayer structures. The method is employed to investigate the structure of a particular surfactant system (didodecyldimethylammonium bromide in a solution of oil and heavy water), for which single-crystal experimental data have recently been collected. The diffracted peak intensities correlate well with theoretical structures based on mathematical minimal surfaces. Optimized electron density profiles of the bilayer are presented, providing new insight into key features of the bilayer structure.

  14. Charge detection in a bilayer graphene quantum dot

    Energy Technology Data Exchange (ETDEWEB)

    Fringes, Stefan; Norda, Caroline; Dauber, Jan; Engels, Stephan [JARA-FIT and II, Institute of Physics B, RWTH Aachen University, 52074 Aachen (Germany); Volk, Christian; Terres, Bernat; Stampfer, Christoph [JARA-FIT and II, Institute of Physics B, RWTH Aachen University, 52074 Aachen (Germany); Peter Gruenberg Institute (PGI-8/9), Forschungszentrum Juelich, 52425 Juelich (Germany); Trellenkamp, Stefan [Peter Gruenberg Institute (PGI-8/9), Forschungszentrum Juelich, 52425 Juelich (Germany)

    2011-11-15

    We show measurements on a bilayer graphene quantum dot (QD) with an integrated charge detector. The focus lies on enabling charge detection with a 30 nm wide bilayer graphene nanoribbon located approximately 35 nm next to a bilayer graphene QD with an island diameter of about 100 nm. Local resonances in the nanoribbon can be successfully used to detect individual charging events in the dot even in regimes where the QD Coulomb peaks cannot be measured by conventional techniques. False color atomic force microscope image of the investigated device. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Spin Hall magnetoresistance in antiferromagnet/normal metal bilayers

    KAUST Repository

    Manchon, Aurelien

    2017-01-01

    We investigate the emergence of spin Hall magnetoresistance in a magnetic bilayer composed of a normal metal adjacent to an antiferromagnet. Based on a recently derived drift diffusion equation, we show that the resistance of the bilayer depends on the relative angle between the direction transverse to the current flow and the Néel order parameter. While this effect presents striking similarities with the spin Hall magnetoresistance recently reported in ferromagnetic bilayers, its physical origin is attributed to the anisotropic spin relaxation of itinerant spins in the antiferromagnet.

  16. Structure and dynamics of H{sub 2}O vis-á-vis phenylalanine recognition at a DPPC lipid membrane via interfacial H-bond types: Insights from polarized FT-IRRAS and ADMP simulations

    Energy Technology Data Exchange (ETDEWEB)

    Sarangi, Nirod Kumar; Ramesh, Nivarthi; Patnaik, Archita [Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036 (India)

    2015-01-14

    Preferential and enantioselective interactions of L-/D-Phenylalanine (L-Phe and D-Phe) and butoxycarbonyl-protected L-/D-Phenylalanine (LPA and DPA) as guest with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (L-DPPC) as host were tapped by using real time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). Polarization-modulated FT-IRRAS of DPPC monolayers above the phenylalanine modified subphases depicted fine structure/conformation differences under considerations of controlled 2D surface pressure. Selective molecular recognition of D-enantiomer over L-enantiomer driven by the DPPC head group via H-bonding and electrostatic interactions was evident spectroscopically. Accordingly, binding constants (K) of 145, 346, 28, and 56 M{sup −1} for LPA, DPA, L-Phe, and D-Phe, respectively, were estimated. The real time FT-IRRAS water bands were strictly conformation sensitive. The effect of micro-solvation on the structure and stability of the 1:1 diastereomeric L-lipid⋯, LPA/DPA and L-lipid⋯, (L/D)-Phe adducts was investigated with the aid of Atom-centered Density Matrix Propagation (ADMP), a first principle quantum mechanical molecular dynamics approach. The phosphodiester fragment was the primary site of hydration where specific solvent interactions were simulated through single- and triple- “water-phosphate” interactions, as water cluster’s “tetrahedral dice” to a “trimeric motif” transformation as a partial de-clusterization was evident. Under all the hydration patterns considered in both static and dynamic descriptions of density functional theory, L-lipid/D-amino acid enantiomer adducts continued to be stable structures while in dynamic systems, water rearranged without getting “squeezed-out” in the process of recognition. In spite of the challenging computational realm of this multiscale problem, the ADMP simulated molecular interactions complying with polarized vibrational spectroscopy unraveled a novel route to chiral

  17. Structure and dynamics of H2O vis-á-vis phenylalanine recognition at a DPPC lipid membrane via interfacial H-bond types: Insights from polarized FT-IRRAS and ADMP simulations

    Science.gov (United States)

    Sarangi, Nirod Kumar; Ramesh, Nivarthi; Patnaik, Archita

    2015-01-01

    Preferential and enantioselective interactions of l-/d-Phenylalanine (l-Phe and d-Phe) and butoxycarbonyl-protected l-/d-Phenylalanine (LPA and DPA) as guest with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (l-DPPC) as host were tapped by using real time Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS). Polarization-modulated FT-IRRAS of DPPC monolayers above the phenylalanine modified subphases depicted fine structure/conformation differences under considerations of controlled 2D surface pressure. Selective molecular recognition of d-enantiomer over l-enantiomer driven by the DPPC head group via H-bonding and electrostatic interactions was evident spectroscopically. Accordingly, binding constants (K) of 145, 346, 28, and 56 M-1 for LPA, DPA, l-Phe, and d-Phe, respectively, were estimated. The real time FT-IRRAS water bands were strictly conformation sensitive. The effect of micro-solvation on the structure and stability of the 1:1 diastereomeric l-lipid⋯, LPA/DPA and l-lipid⋯, (l/d)-Phe adducts was investigated with the aid of Atom-centered Density Matrix Propagation (ADMP), a first principle quantum mechanical molecular dynamics approach. The phosphodiester fragment was the primary site of hydration where specific solvent interactions were simulated through single- and triple- "water-phosphate" interactions, as water cluster's "tetrahedral dice" to a "trimeric motif" transformation as a partial de-clusterization was evident. Under all the hydration patterns considered in both static and dynamic descriptions of density functional theory, l-lipid/d-amino acid enantiomer adducts continued to be stable structures while in dynamic systems, water rearranged without getting "squeezed-out" in the process of recognition. In spite of the challenging computational realm of this multiscale problem, the ADMP simulated molecular interactions complying with polarized vibrational spectroscopy unraveled a novel route to chiral recognition and

  18. The use of virtual ground to control transmembrane voltages and measure bilayer currents in serial arrays of droplet interface bilayers

    Science.gov (United States)

    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.

  19. Sub-wavelength antenna enhanced bilayer graphene tunable photodetector

    Energy Technology Data Exchange (ETDEWEB)

    Beechem, III, Thomas Edwin; Howell, Stephen W.; Peters, David W.; Davids, Paul; Ohta, Taisuke

    2016-03-22

    The integration of bilayer graphene with an absorption enhancing sub-wavelength antenna provides an infrared photodetector capable of real-time spectral tuning without filters at nanosecond timescales.

  20. Capacitance Variation of Electrolyte-Gated Bilayer Graphene Based Transistors

    Directory of Open Access Journals (Sweden)

    Hediyeh Karimi

    2013-01-01

    Full Text Available Quantum capacitance of electrolyte-gated bilayer graphene field-effect transistors is investigated in this paper. Bilayer graphene has received huge attention due to the fact that an energy gap could be opened by chemical doping or by applying external perpendicular electric field. So, this extraordinary property can be exploited to use bilayer graphene as a channel in electrolyte-gated field-effect transistors. The quantum capacitance of bi-layer graphene with an equivalent circuit is presented, and also based on the analytical model a numerical solution is reported. We begin by modeling the DOS, followed by carrier concentration as a function V in degenerate and nondegenerate regimes. To further confirm this viewpoint, the presented analytical model is compared with experimental data, and acceptable agreement is reported.

  1. Tethered and Polymer Supported Bilayer Lipid Membranes: Structure and Function

    Directory of Open Access Journals (Sweden)

    Jakob Andersson

    2016-05-01

    Full Text Available Solid supported bilayer lipid membranes are model systems to mimic natural cell membranes in order to understand structural and functional properties of such systems. The use of a model system allows for the use of a wide variety of analytical tools including atomic force microscopy, impedance spectroscopy, neutron reflectometry, and surface plasmon resonance spectroscopy. Among the large number of different types of model membranes polymer-supported and tethered lipid bilayers have been shown to be versatile and useful systems. Both systems consist of a lipid bilayer, which is de-coupled from an underlying support by a spacer cushion. Both systems will be reviewed, with an emphasis on the effect that the spacer moiety has on the bilayer properties.

  2. Electronic properties of asymmetrically doped twisted graphene bilayers

    Science.gov (United States)

    Trambly de Laissardière, Guy; Namarvar, Omid Faizy; Mayou, Didier; Magaud, Laurence

    2016-06-01

    Rotated graphene bilayers form an exotic class of nanomaterials with fascinating electronic properties governed by the rotation angle θ . For large rotation angles, the electron eigenstates are restricted to one layer and the bilayer behaves like two decoupled graphene layers. At intermediate angles, Dirac cones are preserved but with a lower velocity and van Hove singularities are induced at energies where the two Dirac cones intersect. At very small angles, eigenstates become localized in peculiar moiré zones. We analyze here the effect of an asymmetric doping for a series of commensurate rotated bilayers on the basis of tight-binding calculations of their band dispersions, density of states, participation ratio, and diffusive properties. While a small doping level preserves the θ dependence of the rotated bilayer electronic structure, larger doping induces a further reduction of the band velocity in the same way as a further reduction of the rotation angle.

  3. Pairing of cholesterol with oxidized phospholipid species in lipid bilayers

    DEFF Research Database (Denmark)

    Khandelia, Himanshu; Loubet, Bastien; Olzynska, Agnieszka

    2014-01-01

    We claim that (1) cholesterol protects bilayers from disruption caused by lipid oxidation by sequestering conical shaped oxidized lipid species such as 1-palmitoyl-2-azelaoyl-sn-glycero-3-phosphocholine (PZPC) away from phospholipid, because cholesterol and the oxidized lipid have complementary...... shapes and (2) mixtures of cholesterol and oxidized lipids can self-assemble into bilayers much like lysolipid–cholesterol mixtures. The evidence for bilayer protection comes from molecular dynamics (MD) simulations and dynamic light scattering (DLS) measurements. Unimodal size distributions of extruded...... vesicles (LUVETs) made up of a mixture of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and PZPC containing high amounts of PZPC are only obtained when cholesterol is present in high concentrations. In simulations, bilayers containing high amounts of PZPC become porous, unless cholesterol is also present...

  4. Ion dynamics in cationic lipid bilayer systems in saline solutions

    DEFF Research Database (Denmark)

    Miettinen, Markus S; Gurtovenko, Andrey A; Vattulainen, Ilpo

    2009-01-01

    mixture of cationic dimyristoyltrimethylammoniumpropane (DMTAP) and zwitterionic (neutral) dimyristoylphosphatidylcholine (DMPC) lipids. Using atomistic molecular dynamics simulations, we address the effects of bilayer composition (cationic to zwitterionic lipid fraction) and of NaCl electrolyte...

  5. Bilayer properties of hydroxytyrosol- and tyrosol-phosphatidylcholine lipids

    Science.gov (United States)

    Tyrosol and hydroxytyrosol are the phytochemicals abundantly found in olive oil. Transphosphatidylation of tyrosol and hydroxytyrosol with dioleoylphosphocholine resulted in phospholipids with antioxidant properties. The ability of these phyto-phospholipids to form liposomes and supported bilayers w...

  6. Molecular Dynamics of a Water-Lipid Bilayer Interface

    Science.gov (United States)

    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.

  7. Molecular doping and band-gap opening of bilayer graphene.

    OpenAIRE

    Samuels, AJ; Carey, JD

    2013-01-01

    The ability to induce an energy band gap in bilayer graphene is an important development in graphene science and opens up potential applications in electronics and photonics. Here we report the emergence of permanent electronic and optical band gaps in bilayer graphene upon adsorption of π electron containing molecules. Adsorption of n- or p-type dopant molecules on one layer results in an asymmetric charge distribution between the top and bottom layers and in the formation of an energy gap. ...

  8. A generic model for lipid monolayers, bilayers, and membranes

    CERN Document Server

    Schmid, F; Lenz, O; West, B

    2007-01-01

    We describe a simple coarse-grained model which is suited to study lipid layers and their phase transitions. Lipids are modeled by short semiflexible chains of beads with a solvophilic head and a solvophobic tail component. They are forced to self-assemble into bilayers by a computationally cheap `phantom solvent' environment. The model reproduces the most important phases and phase transitions of monolayers and bilayers. Technical issues such as Monte Carlo parallelization schemes are briefly discussed.

  9. Tunable Fermi surface topology and Lifshitz transition in bilayer graphene

    OpenAIRE

    Varlet, Anastasia; Mucha-Kruczyński, Marcin; Bischoff, Dominik; Simonet, Pauline; Taniguchi, Takashi; Watanabe, Kenji; Fal'ko, Vladimir; Ihn, Thomas; Ensslin, Klaus

    2015-01-01

    Bilayer graphene is a highly tunable material: not only can one tune the Fermi energy using standard gates, as in single-layer graphene, but the band structure can also be modified by external perturbations such as transverse electric fields or strain. We review the theoretical basics of the band structure of bilayer graphene and study the evolution of the band structure under the influence of these two external parameters. We highlight their key role concerning the ease to experimentally pro...

  10. Gates controlled parallel-coupled bilayer graphene double quantum dot

    CERN Document Server

    Wang, Lin-Jun; Wei, Da; Cao, Gang; Tu, Tao; Xiao, Ming; Guo, Guang-Can; Chang, A M

    2011-01-01

    Here we report the fabrication and quantum transport measurements of gates controlled parallel-coupled bilayer graphene double quantum dot. It is shown that the interdot coupling strength of the parallel double dots can be effectively tuned from weak to strong regime by both the in-plane plunger gates and back gate. All the relevant energy scales and parameters of the bilayer graphene parallel-coupled double dot can be extracted from the honeycomb charge stability diagrams revealed through the transport measurements.

  11. Molecular Dynamics of a Water-Lipid Bilayer Interface

    Science.gov (United States)

    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.

  12. Thermodynamic study of benzocaine insertion into different lipid bilayers

    Science.gov (United States)

    Cascales, J. J. López; Costa, S. D. Oliveira; Porasso, R. D.

    2011-10-01

    Despite the general consensus concerning the role played by sodium channels in the molecular mechanism of local anesthetics, the potency of anaesthetic drugs also seems to be related with their solubility in lipid bilayers. In this respect, this work represents a thermodynamic study of benzocaine insertion into lipid bilayers of different compositions by means of molecular dynamics simulation. Thus, the free energy profiles associated with benzocaine insertion into symmetric lipid bilayers composed of different proportions of dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylserine were studied. From the simulation results, a maximum in the free energy (ΔG) profile was measured in the region of the lipid/solution interface. This free energy barrier appears to be very much dependent on the lipid composition of the membrane. On the other hand, the minimum free energy (ΔG) within the bilayer remained almost independent of the lipid composition of the bilayer. By repeating the study at different temperatures, it was seen how the spontaneity of benzocaine insertion into the lipid bilayer is due to an increase in the entropy associated with the process.

  13. Microporous device for local electric recordings on model lipid bilayers

    Science.gov (United States)

    Kaufeld, Theresa; Steinem, Claudia; Schmidt, Christoph F.

    2015-01-01

    A powerful approach for characterizing lipid membranes and embedded proteins is the reconstitution of model lipid bilayers. The extreme fragility of 5 nm thick bilayers is a challenge for device design and requires a trade off of stability against accessibility. We here present a microporous lab-on-chip device that allows us to form stable, solvent-free lipid bilayers from giant unilamellar vesicles (GUVs) in a geometry that provides a unique set of access possibilities. The device is constructed around a micro-fabricated silicon chip with clusters of 1 µm-diameter pores and provides optical access to the lipid bilayers for high-NA epifluorescence imaging. At the same time, solvent exchange is possible on both sides of the lipid bilayer. Complete coverage can be achieved with GUVs, so that voltages can be applied across the lipid bilayer and single-channel currents can be measured using external or integrated silver/silver chloride electrodes. We describe the micro-fabrication by standard cleanroom techniques and the characterization of the device by atomic force microscopy, scanning electron microscopy and impedance spectroscopy. In proof-of-concept experiments we demonstrate that the device is capable of low-noise, single-ion-channel recordings. Electronic Supplementary Information (ESI) available: See DOI: 10.1039/b000000x/

  14. Robustly Engineering Thermal Conductivity of Bilayer Graphene by Interlayer Bonding.

    Science.gov (United States)

    Zhang, Xiaoliang; Gao, Yufei; Chen, Yuli; Hu, Ming

    2016-02-25

    Graphene and its bilayer structure are the two-dimensional crystalline form of carbon, whose extraordinary electron mobility and other unique features hold great promise for nanoscale electronics and photonics. Their realistic applications in emerging nanoelectronics usually call for thermal transport manipulation in a controllable and precise manner. In this paper we systematically studied the effect of interlayer covalent bonding, in particular different interlay bonding arrangement, on the thermal conductivity of bilayer graphene using equilibrium molecular dynamics simulations. It is revealed that, the thermal conductivity of randomly bonded bilayer graphene decreases monotonically with the increase of interlayer bonding density, however, for the regularly bonded bilayer graphene structure the thermal conductivity possesses unexpectedly non-monotonic dependence on the interlayer bonding density. The results suggest that the thermal conductivity of bilayer graphene depends not only on the interlayer bonding density, but also on the detailed topological configuration of the interlayer bonding. The underlying mechanism for this abnormal phenomenon is identified by means of phonon spectral energy density, participation ratio and mode weight factor analysis. The large tunability of thermal conductivity of bilayer graphene through rational interlayer bonding arrangement paves the way to achieve other desired properties for potential nanoelectronics applications involving graphene layers.

  15. PI3 kinase enzymology on fluid lipid bilayers.

    Science.gov (United States)

    Dutta, Debjit; Pulsipher, Abigail; Luo, Wei; Yousaf, Muhammad N

    2014-10-21

    We report the use of fluid lipid bilayer membrane as a model platform to study the influence of the bilayer microenvironment and composition on the enzymology in membrane. As a model system we determined the enzyme kinetics on membranes for the transformation of bilayers containing phosphoinositol(4,5)-bisphosphate (PI(4,5)P2) to phosphoinositol(3,4,5)-trisphosphate (PI(3,4,5)P3) by the enzyme phosphoinositol-3-kinase (PI3K) using radiolabeled ATP. The activity of the enzyme was monitored as a function of the radioactivity incorporated within the bilayer. The transformation of PI(4,5)P2 to PI(3,4,5)P3 was determined using a mass strip assay. The fluidity of the bilayer was confirmed by Fluorescence Recovery After Photobleaching (FRAP) experiments. Kinetic simulations were performed based on Langmuir adsorption and Michaelis-Menton kinetics equations to generate the rate constants for the enzymatic reaction. The effect of cholesterol on the enzyme kinetics was studied by doping the bilayer with 1% cholesterol. This leads to significant reduction in reaction rate due to change in membrane microenvironment. This strategy provides a method to study the enzymology of various kinases and phosphatases occurring at the membrane and also how these reactions are affected by the membrane composition and surface microenvironment.

  16. Different oxidized phospholipid molecules unequally affect bilayer packing.

    Science.gov (United States)

    Megli, Francesco M; Russo, Luciana

    2008-01-01

    The aim of this study was to gain more detailed knowledge about the effect of the presence of defined oxidized phospholipid molecules in phospholipid bilayers. After chromatographic and mass spectrometry analysis, the previously used product of the Fenton reaction with unsaturated lecithins proved to consist of a plethora of oxidatively modified lecithins, useless either for the detailed study of the effects brought about in the bilayer or as the source of defined oxidized phospholipid molecules. The latter, particularly 2-(omega-carboxyacyl)- and 2-(n-hydroperoxyacyl)-lecithins, can be more conveniently prepared by chemical or enzymatic synthesis rather than by chemical or physical oxidation. The effect of those molecules and of commercially available 12-hydroxy-stearic and dodecanedioic acid was studied in planar supported phospholipid bilayers (SPBs) by use of EPR spectrometry. The SPBs also contained 2-(5-doxylstearoyl)-lecithin as the spin probe, and the EPR spectral anisotropy loss, indicative of bilayer disordering, was measured as a function of the molar percentage of oxidized lipid. Most oxidized lipid molecules examined in this study were able to induce bilayer disordering, while hydroperoxyl group-bearing acyl chains appeared to be much less effective. It is concluded that the effects of different oxidized phospholipids on phospholipid bilayer structure cannot be generalized, as happens with batch-oxidized phospholipids, and that the use of defined oxidized phospholipid molecular species for membrane oxidative stress guarantees a more reliable and detailed response.

  17. Mechanism of unassisted ion transport across membrane bilayers

    Science.gov (United States)

    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.

  18. Amphiphile regulation of ion channel function by changes in the bilayer spring constant

    DEFF Research Database (Denmark)

    Lundbæk, Jens August; Koeppe, R.E.; Andersen, Oluf Sten

    2010-01-01

    be predicted from measurements of isolated changes in such properties. Thus, the bilayer contribution to the promiscuous regulation of membrane proteins by drugs and other amphiphiles remains unknown. To overcome this problem, we use gramicidin A (gA) channels as molecular force probes to measure the net......Many drugs are amphiphiles that, in addition to binding to a particular target protein, adsorb to cell membrane lipid bilayers and alter intrinsic bilayer physical properties (e. g., bilayer thickness, monolayer curvature, and elastic moduli). Such changes can modulate membrane protein function...... by altering the energetic cost (Delta G(bilayer)) of bilayer deformations associated with protein conformational changes that involve the protein-bilayer interface. But amphiphiles have complex effects on the physical properties of lipid bilayers, meaning that the net change in Delta G(bilayer) cannot...

  19. Calorimetric studies of the effect of -carotenoids on the thermotropic phase behavior of phosphatidylcholine bilayers

    OpenAIRE

    Widomska, Justyna; Kostecka-Gugała, Anna; Latowski, Dariusz; Gruszecki, Wiesław I.; Strzałka, Kazimierz

    2009-01-01

    Abstract Carotenoid geometry is a factor that determines their solubility and orientation in the lipid memebrane as well as antioxidant capacities and bioavailability. The effects of the cis-isomers of carotenoids (zeaxanthin and ?-carotene) on the thermotropic properties of lipid membranes formed with dimyristoylphosphatidylcholine (DMPC) and dipalmitoylphosphatidylcholine (DPPC) were investigated by means of differential scanning calorimetry. The results were compared with the ef...

  20. Condensation energy of the superconducting bilayer cuprates

    Indian Academy of Sciences (India)

    Govind; Ajay; S K Joshi

    2002-05-01

    In the present work, we report the interplay of single particle and Cooper pair tunnelings on the superconducting state of layered high-c cuprate superconductors. For this we have considered a model Hamiltonian incorporating the intra-planar interactions and the contributions arising due to the coupling between the planes. The interplanar interactions include the single particle tunneling as well as the Josephson tunneling of Cooper pairs between the two layers. The expression of the out-of-plane correlation parameter which describes the hopping of a particle from one layer to another layer in the superconducting state is obtained within a Bardeen–Cooper–Schriefer (BCS) formalism using the Green’s function technique. This correlation is found to be sensitive to the various parameter of the model Hamiltonian. We have calculated the out-of-plane contribution to the superconducting condensation energy. The calculated values of condensation energy are in agreement with those obtained from the specific heat and the -axis penetration depth measurements on bilayer cuprates.

  1. Titration force microscopy on supported lipid bilayers.

    Science.gov (United States)

    Garcia-Manyes, Sergi; Gorostiza, Pau; Sanz, Fausto

    2006-01-01

    The use of chemically modified atomic force microscopy (AFM) probes allows us to measure the surface charges of supported planar lipid bilayers with high sensitivity through the force spectroscopy operation mode. By controlling the chemistry of the tip, we can perform a classical analytical chemistry titration where the titration agent is a weak acid (attached to the AFM tip) with the particularity of being performed in surface rather than in solution and, especially, at the nanometric scale. Thus, the AFM tip acts as a real "nanosensor". The approaching curves of the force plots reveal that electrostatic interactions between the tip and the supported membrane play a key role. Besides, the plot of the adhesion force (measured from the retracting curve of the force plots) versus pH displays a nonsigmoidal shape with a peak in the adhesion force attributed to high-energy hydrogen bonds. One of these peaks corresponds to the pKa of the surface under study and the other to the pKa of the titrating probe attached to the tip.

  2. Exceptional Optoelectronic Properties of Hydrogenated Bilayer Silicene

    Directory of Open Access Journals (Sweden)

    Bing Huang

    2014-05-01

    Full Text Available Silicon is arguably the best electronic material, but it is not a good optoelectronic material. By employing first-principles calculations and the cluster-expansion approach, we discover that hydrogenated bilayer silicene (BS shows promising potential as a new kind of optoelectronic material. Most significantly, hydrogenation converts the intrinsic BS, a strongly indirect semiconductor, into a direct-gap semiconductor with a widely tunable band gap. At low hydrogen concentrations, four ground states of single- and double-sided hydrogenated BS are characterized by dipole-allowed direct (or quasidirect band gaps in the desirable range from 1 to 1.5 eV, suitable for solar applications. At high hydrogen concentrations, three well-ordered double-sided hydrogenated BS structures exhibit direct (or quasidirect band gaps in the color range of red, green, and blue, affording white light-emitting diodes. Our findings open opportunities to search for new silicon-based light-absorption and light-emitting materials for earth-abundant, high-efficiency, optoelectronic applications.

  3. Properties of bilayer contacts to porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Gallach, D.; Torres-Costa, V.; Garcia-Pelayo, L.; Climent-Font, A.; Martin-Palma, R.J.; Manso, M. [Universidad Autonoma de Madrid, Departamento de Fisica Aplicada, Madrid (Spain); Barreiros-das-Santos, M.; Sporer, C.; Samitier, J. [Institute for Bioengineering of Catalonia (IBEC), Nanobioengineering Group, Barcelona (Spain)

    2012-05-15

    The aim of the present work is the growth by PVD techniques and ulterior characterization of electrical contacts to columnar porous silicon (PSi) as an approach to reliable PSi sensor devices. Contacts consist of a NiCr (40:60) and Au bilayer on the PSi surface deposited by magnetron sputtering. These structures show a good adhesion to the rough surface of columnar PSi. The morphology of these electrical contacts is characterized by electron microscopy and their crystalline structure by X-ray diffraction. Compositional profiles are determined by Rutherford backscattering spectroscopy and energy dispersive X-ray spectroscopy, which demonstrate that the infiltration of NiCr into the PSi is at the origin of the metallic thin film adhesion improvement. I-V characteristics and impedance spectroscopy measurements show that this configuration provides rectifying electrical contacts to PSi, for which a simple equivalent circuit based on one resistor and two capacitors can be modeled. These results further support the use of PSi electrical structures for sensing purposes. (orig.)

  4. Raman modes in transferred bilayer CVD graphene

    Directory of Open Access Journals (Sweden)

    Niilisk Ahti

    2015-01-01

    Full Text Available A systematic experimental Raman spectroscopic study of twisted bilayer graphene (tBLG domains localized inside wide-area single layer graphene (SLG produced by low-pressure CVD on Cu foil and transferred onto SiO2/Si substrate has been performed. According to the Raman characterization the tBLG domains had a great variety of twisting angles θ between the bottom and top graphene layers (6° < θ < 25°. The twisting angle θ was estimated from the spectral position of the rotating R and R' modes in the Raman spectrum.Under G band resonance conditions the breathing mode ZO' with a frequency of 95- 97 cm−1 was detected, and a breathing mode ZO was found in the spectra between 804 cm−1 and 836 cm−1, its position depending on the twisting angle θ. An almost linear relationship was found between the frequencies ωZO and ωR. Also a few other spectral peculiarities were found, e.g. a high-energy excitation of the G band resonance, the 2G overtone appearing at 3170-3180 cm−1 by the G band resonance, revealing a linear dispersion of 80 cm−1/eV of the 2D band in tBLG

  5. Pattern Formation in Dewetting Nanoparticle/Polymer Bilayers

    Science.gov (United States)

    Esker, Alan; Paul, Rituparna; Karabiyik, Ufuk; Swift, Michael; Hottle, John

    2008-03-01

    Comprised of inorganic cores and flexible organic coronae with 1 -- 2 nm diameter monodisperse sizes, polyhedral oligomeric silsesquioxanes (POSS) are ideal model nanofillers. Our discovery that one POSS derivative, trisilanolphenyl-POSS (TPP), can form Langmuir-Blodgett (LB) films on hydrophobic substrates, allows us to create thin film bilayers of precisely controlled thickness and architecture. Work with poly(t-butylacrylate) (PtBA)/TPP bilayers reveals a two-step dewetting mechanism in which the upper TPP layer dewets first, followed by the formation of isolated holes with intricate, fractal, nanofiller aggregates. Like the PtBA/TPP bilayers, polystyrene (PS)/TPP bilayers also undergo a two-step dewetting mechanism. However, the upper TPP layer initially forms cracks that may arise from mismatches in thermal expansion coefficients. These cracks then serve as nucleation sites for complete dewetting of the entire bilayer. Understanding the rich diversity of surface patterns that can be formed from relatively simple processes is a key feature of this work.

  6. Sensitivity analysis of bi-layered ceramic dental restorations.

    Science.gov (United States)

    Zhang, Zhongpu; Zhou, Shiwei; Li, Qing; Li, Wei; Swain, Michael V

    2012-02-01

    The reliability and longevity of ceramic prostheses have become a major concern. The existing studies have focused on some critical issues from clinical perspectives, but more researches are needed to address fundamental sciences and fabrication issues to ensure the longevity and durability of ceramic prostheses. The aim of this paper was to explore how "sensitive" the thermal and mechanical responses, in terms of changes in temperature and thermal residual stress of the bi-layered ceramic systems and crown models will be with respect to the perturbation of the design variables chosen (e.g. layer thickness and heat transfer coefficient) in a quantitative way. In this study, three bi-layered ceramic models with different geometries are considered: (i) a simple bi-layered plate, (ii) a simple bi-layer triangle, and (iii) an axisymmetric bi-layered crown. The layer thickness and convective heat transfer coefficient (or cooling rate) seem to be more sensitive for the porcelain fused on zirconia substrate models. The resultant sensitivities indicate a critical importance of the heat transfer coefficient and thickness ratio of core to veneer on the temperature distributions and residual stresses in each model. The findings provide a quantitative basis for assessing the effects of fabrication uncertainties and optimizing the design of ceramic prostheses. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  7. Thermal Response Analysis of Phospholipid Bilayers Using Ellipsometric Techniques.

    Science.gov (United States)

    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.

  8. Thermotropic phase behaviour of alpha-dipalmitoylphosphatidylcholine multibilayers is influenced to various extents by carotenoids containing different structural features--evidence from differential scanning calorimetry.

    Science.gov (United States)

    Kostecka-Gugała, Anna; Latowski, Dariusz; Strzałka, Kazimierz

    2003-01-31

    Carotenoids are the effective modulators of physical properties of model and natural membranes. To demonstrate the relationship between the structure of carotenoids and their effect on the molecular dynamics of membranes, we have investigated the influence of five structurally different carotenoids: beta-carotene, lycopene, lutein, violaxanthin, zeaxanthin and additionally carotane--a fully saturated derivative of beta-carotene, on thermotropic phase behaviour of dipalmitoylphosphatidylcholine (DPPC) multilamellar vesicles by means of differential scanning calorimetry (DSC). The results obtained indicate that the carotenoids used modulated the thermotropic properties of multibilayers to various extents, broadening the pretransition and the main phase transition peaks and shifting them to lower temperatures. Pronounced decrease of pretransition enthalpy (DeltaH(p)) proves that carotenoids very strongly alter the membrane properties in its gel phase. Comparison of the influence of several carotenoids shows that a rigid, polyisoprenoid chain plays a basic role in altering the thermotropic properties of such membranes and the presence of rings without oxygen-containing groups has a minor significance for the observed interactions. Carotenoids containing epoxy and/or hydroxy groups attached to their rings modify the thermotropic phase behaviour of DPPC multilamellar vesicles stronger than carotenes--a result of their orientation in the DPPC bilayer.

  9. Molecular-dynamics simulation of a ceramide bilayer

    Science.gov (United States)

    Pandit, Sagar A.; Scott, H. Larry

    2006-01-01

    Ceramide is the simplest lipid in the biologically important class of glycosphingolipids. Ceramide is an important signaling molecule and a major component of the strateum corneum layer in the skin. In order to begin to understand the biophysical properties of ceramide, we have carried out a molecular-dynamics simulation of a hydrated 16:0 ceramide lipid bilayer at 368K (5° above the main phase transition). In this paper we describe the simulation and present the resulting properties of the bilayer. We compare the properties of the simulated ceramide bilayer to an earlier simulation of 18:0 sphingomyelin, and we discuss the results as they relate to experimental data for ceramide and other sphingolipids. The most significant differences arise at the lipid/water interface, where the lack of a large ceramide polar group leads to a different electron density and a different electrostatic potential but, surprisingly, not a different overall "dipole potential," when ceramide is compared to sphingomyelin.

  10. Meron-Pair Excitations in Bilayer Quantum Hall System

    Science.gov (United States)

    Moon, Kyungsun

    Bilayer two-dimensional electron gas systems can form unusual broken symmetry states with spontaneous inter-layer phase coherence at certain filling factors. At total filling factor νT = 1, the lowest energy charged excitation of the system is theoretically suggested to be a linearly-confined meron-pair, which is topologically identical to a single skyrmion. We will review how this remarkable excitation arises and can help unravel various experimental results demonstrated in bilayer quantum Hall system. In order to detect the linearly-confined meron-pair excitation directly, we propose a gated bilayer Hall bar experiment, where the magnitude and orientation of magnetic field B‖ applied parallel to the 2D plane can be controlled. We demonstrate a strong angle-dependent transport due to the anisotropic nature of linearly-confined meron-pairs and discuss how it would be manifested in experiment.

  11. Equilibrium Configurations of Lipid Bilayer Membranes and Carbon Nanostructures

    Institute of Scientific and Technical Information of China (English)

    Iva(i)lo M.Mladenov; Peter A.Djondjorov; Mariana Ts.Hadzhilazova; Vassil M.Vassilev

    2013-01-01

    The present article concerns the continuum modelling of the mechanical behaviour and equilibrium shapes of two types of nano-scale objects:fluid lipid bilayer membranes and carbon nanostructures.A unified continuum model is used to handle four different case studies.Two of them consist in representing in analytic form cylindrical and axisymmetric equilibrium configurations of single-wall carbon nanotubes and fluid lipid bilayer membranes subjected to uniform hydrostatic pressure.The third one is concerned with determination of possible shapes of junctions between a single-wall carbon nanotube and a fiat graphene sheet or another single-wall carbon nanotube.The last one deals with the mechanical behaviour of closed fluid lipid bilayer membranes (vesicles) adhering onto a fiat homogeneous rigid substrate subjected to micro-injection and uniform hydrostatic pressure.

  12. Curvatronics with bilayer graphene in an effective $4D$ spacetime

    CERN Document Server

    Cariglia, M; Perali, A

    2016-01-01

    We show that in AB stacked bilayer graphene low energy excitations around the semimetallic points are described by massless, four dimensional Dirac fermions. There is an effective reconstruction of the 4 dimensional spacetime, including in particular the dimension perpendicular to the sheet, that arises dynamically from the physical graphene sheet and the interactions experienced by the carriers. The effective spacetime is the Eisenhart-Duval lift of the dynamics experienced by Galilei invariant L\\'evy-Leblond spin $\\frac{1}{2}$ particles near the Dirac points. We find that changing the intrinsic curvature of the bilayer sheet induces a change in the energy level of the electronic bands, switching from a conducting regime for negative curvature to an insulating one when curvature is positive. In particular, curving graphene bilayers allows opening or closing the energy gap between conduction and valence bands, a key effect for electronic devices. Thus using curvature as a tunable parameter opens the way for t...

  13. Exchange bias training effect in coupled all ferromagnetic bilayer structures.

    Science.gov (United States)

    Binek, Ch; Polisetty, S; He, Xi; Berger, A

    2006-02-17

    Exchange coupled bilayers of soft and hard ferromagnetic thin films show remarkable analogies to conventional antiferromagnetic/ferromagnetic exchange bias heterostructures. Not only do all these ferromagnetic bilayers exhibit a tunable exchange bias effect, they also show a distinct training behavior upon cycling the soft layer through consecutive hysteresis loops. In contrast with conventional exchange bias systems, such all ferromagnetic bilayer structures allow the observation of training induced changes in the bias-setting hardmagnetic layer by means of simple magnetometry. Our experiments show unambiguously that the exchange bias training effect is driven by deviations from equilibrium in the pinning layer. A comparison of our experimental data with predictions from a theory based upon triggered relaxation phenomena shows excellent agreement.

  14. Laurdan fluorescence senses mechanical strain in the lipid bilayer membrane.

    Science.gov (United States)

    Zhang, Yan-Liang; Frangos, John A; Chachisvilis, Mirianas

    2006-09-01

    The precise molecular mechanisms by which cells transduce a mechanical stimulus into an intracellular biochemical response have not yet been established. Here, we show for the first time that the fluorescence emission of an environment-sensitive membrane probe Laurdan is modulated by mechanical strain of the lipid bilayer membrane. We have measured fluorescence emission of Laurdan in phospholipid vesicles of 30, 50, and 100 nm diameter to show that osmotically induced membrane tension leads to an increase in polarity (hydration depth) of the phospholipid bilayer interior. Our data indicate that the general polarization of Laurdan emission is linearly dependent on membrane tension. We also show that higher membrane curvature leads to higher hydration levels. We anticipate that the proposed method will facilitate future studies of mechanically induced changes in physical properties of lipid bilayer environment both in vitro and in vivo.

  15. Neutron diffraction studies of amphipathic helices in phospholipid bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Bradshaw, J.P.; Gilchrist, P.J. [Univ. of Edinburgh (United Kingdom); Duff, K.C. [Univ. of Edinburgh Medical School (United Kingdom); Saxena, A.M. [Brookhaven National Laboratory, Upton, NY (United States)

    1994-12-31

    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 to 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.

  16. Bilayer Deformation, Pores, and Micellation Induced by Oxidized Lipids.

    Science.gov (United States)

    Boonnoy, Phansiri; Jarerattanachat, Viwan; Karttunen, Mikko; Wong-Ekkabut, Jirasak

    2015-12-17

    The influence of different oxidized lipids on lipid bilayers was investigated with 16 individual 1 μs atomistic molecular dynamics (MD) simulations. Binary mixtures of lipid bilayers of 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphatidylcholine (PLPC) and its peroxide and aldehyde products were performed at different concentrations. In addition, an asymmetrical short chain lipid, 1-palmitoyl-2-decanoyl-sn-glycero-3-phosphatidylcholine (PDPC), was used to compare the effects of polar/apolar groups in the lipid tail on lipid bilayer. Although water defects occurred with both aldehyde and peroxide lipids, full pore formation was observed only for aldehyde lipids. At medium concentrations the pores were stable. At higher concentrations, however, the pores became unstable and micellation occurred. Data analysis shows that aldehyde lipids' propensity for pore formation is due to their shorter and highly mobile tail. The highly polar peroxide lipids are stabilized by strong hydrogen bonds with interfacial water.

  17. Magnetically Assisted Bilayer Composites for Soft Bending Actuators

    Directory of Open Access Journals (Sweden)

    Sung-Hwan Jang

    2017-06-01

    Full Text Available 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.

  18. Manipulating interface states in monolayer-bilayer graphene planar junctions

    Science.gov (United States)

    Zhao, Fang; Xu, Lei; Zhang, Jun

    2016-05-01

    We report on transport properties of monolayer-bilayer graphene planar junctions in a magnetic field. Due to its unique geometry, the edge and interface states can be independently manipulated by either interlayer potential or Zeeman field, and the conductance exhibits interesting quantized behaviors. In the hybrid graphene junction, the quantum Hall (QH) conductance is no longer antisymmetric with respect to the charge neutrality point. When the Zeeman field is considered, a quantum spin Hall (QSH) phase is found in the monolayer region while the weak-QSH phase stays in the bilayer region. In the presence of both interlayer potential and Zeeman field, the bilayer region hosts a QSH phase, whereas the monolayer region is still in a QH phase, leading to a spin-polarized current in the interface. In particular, the QSH phase remains robust against the disorder.

  19. Light-Patterned Current Generation in a Droplet Bilayer Array

    Science.gov (United States)

    Restrepo Schild, Vanessa; Booth, Michael J.; Box, Stuart J.; Olof, Sam N.; Mahendran, Kozhinjampara R.; Bayley, Hagan

    2017-04-01

    We have created a 4 × 4 droplet bilayer array comprising light-activatable aqueous droplet bio-pixels. Aqueous droplets containing bacteriorhodopsin (bR), a light-driven proton pump, were arranged on a common hydrogel surface in lipid-containing oil. A separate lipid bilayer formed at the interface between each droplet and the hydrogel; each bilayer then incorporated bR. Electrodes in each droplet simultaneously measured the light-driven proton-pumping activities of each bio-pixel. The 4 × 4 array derived by this bottom-up synthetic biology approach can detect grey-scale images and patterns of light moving across the device, which are transduced as electrical current generated in each bio-pixel. We propose that synthetic biological light-activatable arrays, produced with soft materials, might be interfaced with living tissues to stimulate neuronal pathways.

  20. Lipid bilayer microarray for parallel recording of transmembrane ion currents.

    Science.gov (United States)

    Le Pioufle, Bruno; Suzuki, Hiroaki; Tabata, Kazuhito V; Noji, Hiroyuki; Takeuchi, Shoji

    2008-01-01

    This paper describes a multiwell biochip for simultaneous parallel recording of ion current through transmembrane pores reconstituted in planar lipid bilayer arrays. Use of a thin poly(p-xylylene) (parylene) film having micrometer-sized apertures (phi=15-50 microm, t=20 microm) led to formation of highly stable bilayer lipid membranes (BLMs) for incorporation of transmembrane pores; thus, a large number of BLMs could be arrayed without any skillful technique. We optically confirmed the simultaneous formation of BLMs in a 5x5 matrix, and in our durability test, the BLM lasted more than 15 h. Simultaneous parallel recording of alamethicin and gramicidin transmembrane pores in multiple contiguous recording sites demonstrated the feasibility of high-throughput screening of transmembrane ion currents in artificial lipid bilayers.

  1. Electro-absorption of silicene and bilayer graphene quantum dots

    Science.gov (United States)

    Abdelsalam, Hazem; Talaat, Mohamed H.; Lukyanchuk, Igor; Portnoi, M. E.; Saroka, V. A.

    2016-07-01

    We study numerically the optical properties of low-buckled silicene and AB-stacked bilayer graphene quantum dots subjected to an external electric field, which is normal to their surface. Within the tight-binding model, the optical absorption is calculated for quantum dots, of triangular and hexagonal shapes, with zigzag and armchair edge terminations. We show that in triangular silicene clusters with zigzag edges a rich and widely tunable infrared absorption peak structure originates from transitions involving zero energy states. The edge of absorption in silicene quantum dots undergoes red shift in the external electric field for triangular clusters, whereas blue shift takes place for hexagonal ones. In small clusters of bilayer graphene with zigzag edges the edge of absorption undergoes blue/red shift for triangular/hexagonal geometry. In armchair clusters of silicene blue shift of the absorption edge takes place for both cluster shapes, while red shift is inherent for both shapes of the bilayer graphene quantum dots.

  2. Binding of cationic peptides (KX)4K to DPPG bilayers. Increasing the hydrophobicity of the uncharged amino acid X drives formation of membrane bound β-sheets: A DSC and FT-IR study.

    Science.gov (United States)

    Hädicke, André; Blume, Alfred

    2016-06-01

    The binding of cationic peptides of the sequence (KX)4K to lipid vesicles of negatively charged dipalmitoyl-phosphatidylglycerol (DPPG) was investigated by differential scanning calorimetry (DSC) and temperature dependent Fourier-transformed infrared (FT-IR) spectroscopy. The hydrophobicity of the uncharged amino acid X was changed from G (glycine) over A (alanine), Abu (α-aminobutyric acid), V (valine) to L (leucine). The binding of the peptides caused an increase of the phase transition temperature (Tm) of DPPG by up to 20°C. The shift depended on the charge ratio and on the hydrophobicity of the amino acid X. Unexpectedly, the upward shift of Tm increased with increasing hydrophobicity of X. FT-IR spectroscopy showed a shift of the CH2 stretching vibrations of DPPG to lower frequency, particularly for bilayers in the liquid-crystalline phase, indicating an ordering of the hydrocarbon chains when the peptides were bound. Changes in the lipid C=O vibrational band indicated a dehydration of the lipid headgroup region after peptide binding. (KG)4K was bound in an unordered structure at all temperatures. All other peptides formed intermolecular antiparallel β-sheets, when bound to gel phase DPPG. However, for (KA)4K and (KAbu)4K, the β-sheets converted into an unordered structure above Tm. In contrast, the β-sheet structures of (KV)4K and (KL)4K remained stable even at 80°C when bound to the liquid-crystalline phase of DPPG. Strong aggregation of DPPG vesicles occurred after peptide binding. For the aggregates, we suggest a structure, where aggregated single β-sheets are sandwiched between opposing DPPG bilayers with a dehydrated interfacial region.

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

    DEFF Research Database (Denmark)

    Rønnest, A. K.; Peters, Günther H.J.; Hansen, Flemming Yssing

    2016-01-01

    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...

  4. Experimental and theoretical evidence for bilayer-by-bilayer surface melting of crystalline ice

    Science.gov (United States)

    Sánchez, M. Alejandra; Kling, Tanja; Ishiyama, Tatsuya; van Zadel, Marc-Jan; Mezger, Markus; Jochum, Mara N.; Cyran, Jenée D.; Smit, Wilbert J.; Bakker, Huib J.; Shultz, Mary Jane; Morita, Akihiro; Donadio, Davide; Nagata, Yuki; Bonn, Mischa; Backus, Ellen H. G.

    2017-01-01

    On the surface of water ice, a quasi-liquid layer (QLL) has been extensively reported at temperatures below its bulk melting point at 273 K. Approaching the bulk melting temperature from below, the thickness of the QLL is known to increase. To elucidate the precise temperature variation of the QLL, and its nature, we investigate the surface melting of hexagonal ice by combining noncontact, surface-specific vibrational sum frequency generation (SFG) spectroscopy and spectra calculated from molecular dynamics simulations. Using SFG, we probe the outermost water layers of distinct single crystalline ice faces at different temperatures. For the basal face, a stepwise, sudden weakening of the hydrogen-bonded structure of the outermost water layers occurs at 257 K. The spectral calculations from the molecular dynamics simulations reproduce the experimental findings; this allows us to interpret our experimental findings in terms of a stepwise change from one to two molten bilayers at the transition temperature. PMID:27956637

  5. Anomalous Hall effect in Fe/Gd bilayers

    KAUST Repository

    Xu, W. J.

    2010-04-01

    Non-monotonic dependence of anomalous Hall resistivity on temperature and magnetization, including a sign change, was observed in Fe/Gd bilayers. To understand the intriguing observations, we fabricated the Fe/Gd bilayers and single layers of Fe and Gd simultaneously. The temperature and field dependences of longitudinal resistivity, Hall resistivity and magnetization in these films have also been carefully measured. The analysis of these data reveals that these intriguing features are due to the opposite signs of Hall resistivity/or spin polarization and different Curie temperatures of Fe and Gd single-layer films. Copyright (C) EPLA, 2010

  6. Bilayer polymer/oxide coating for electroluminescent organic semiconductors

    DEFF Research Database (Denmark)

    Tavares, Luciana

    Organic materials have been given much attention due to their intriguing properties that can be tailored via synthetic chemistry for specific applications combined with their low price and fairly straight-forward large-scale synthesis. Para-hexaphenylene (p6P) nanofibers emit polarized light...... of the fibers with oxygen. We have developed a bilayer coating that does not change significantly the p6P spectrum but strongly reduces bleaching. This bilayer coating consists of a first layer of a stable polymer (PMMA) on top of the organic nanofibers as a protecting layer for avoiding modifications of the p6...

  7. Magnetic properties of a doped graphene-like bilayer

    Energy Technology Data Exchange (ETDEWEB)

    Guo, An-Bang [School of Science, Shenyang University of Technology, Shenyang 110870 (China); Jiang, Wei, E-mail: weijiang.sut.edu@gmail.com [School of Science, Shenyang University of Technology, Shenyang 110870 (China); Zhang, Na [Shenyang Normal University, Shenyang 110034 (China)

    2017-05-15

    A doped graphene-like bilayer is described using a four-sublattice Heisenberg model both ferromagnetic and antiferrimagnetic couplings. The magnetic properties of the bilayer system are studied using the Heisenberg model, retarded Green's function and the linear spin-wave approximation. The spin-wave spectra, energy gap, and the magnetization and quantum fluctuation of the system at the ground state are calculated with various intra- and interlayer couplings. The results indicate that the effect of antiferromagnetic exchange coupling on the magnetic properties of the system is significant. Magnetizations at low temperature show intersection points due to the quantum effects.

  8. Phospholipid bilayer formation at a bare Si surface

    DEFF Research Database (Denmark)

    Gutberlet, T.; Steitz, R.; Fragneto, G.;

    2004-01-01

    Neutron reflectivity was applied to monitor in situ the adsorption of small unilamellar phospholipid vesicles on a solid bare hydrophilic Si interface. The obtained reflectivity curves are consistent with the rupture and fusion model for the adsorption of phosphatidylcholine vesicles to solid...... interfaces. The results show details of the adsorbed bilayer system at ångström resolution and indicate the presence of a thin ∼6 Å thick water leaflet that separates the bilayer from the Si surface. The resolved structural details provide the basis for further investigation of processes such as adsorption...

  9. Prediction of superconductivity in Li-intercalated bilayer phosphorene

    Energy Technology Data Exchange (ETDEWEB)

    Huang, G. Q. [Department of Physics, Nanjing Normal University, Nanjing 210023 (China); National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Xing, Z. W., E-mail: zwxing@nju.edu.cn [National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Xing, D. Y. [National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093 (China); Collaborative Innovation Center of Advanced Microstructures and Department of Physics, Nanjing University, Nanjing 210093 (China)

    2015-03-16

    It is shown that bilayer phosphorene can be transformed from a direct-gap semiconductor to a BCS superconductor by intercalating Li atoms. For the Li-intercalated bilayer phosphorene, we find that the electron occupation of Li-derived band is small and superconductivity is intrinsic. With increasing the intercalation of Li atoms, both increased metallicity and strong electron-phonon coupling are favorable for the enhancement of superconductivity. The obtained electron-phonon coupling λ can be larger than 1 and the superconducting temperature T{sub c} can be increased up to 16.5 K, suggesting that phosphorene may be a good candidate for a nanoscale superconductor.

  10. Bias induced modulation of electrical and thermal conductivity and heat capacity of BN and BN/graphene bilayers

    Science.gov (United States)

    Chegel, Raad

    2017-04-01

    By using the tight binding approximation and Green function method, the electronic structure, density of state, electrical conductivity, heat capacity of BN and BN/graphene bilayers are investigated. The AA-, AB1- and AB2- BN/graphene bilayers have small gap unlike to BN bilayers which are wide band gap semiconductors. Unlike to BN bilayer, the energy gap of graphene/BN bilayers increases with external field. The magnitude of the change in the band gap of BN bilayers is much higher than the graphene/BN bilayers. Near absolute zero, the σ(T) is zero for BN bilayers and it increases with temperature until reaches maximum value then decreases. The BN/graphene bilayers have larger electrical conductivity larger than BN bilayers. For both bilayers, the specific heat capacity has a Schottky anomaly.

  11. Bias induced modulation of electrical and thermal conductivity and heat capacity of BN and BN/graphene bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Chegel, Raad, E-mail: Raad.chegel@gmail.com

    2017-04-15

    By using the tight binding approximation and Green function method, the electronic structure, density of state, electrical conductivity, heat capacity of BN and BN/graphene bilayers are investigated. The AA-, AB{sub 1}- and AB{sub 2}- BN/graphene bilayers have small gap unlike to BN bilayers which are wide band gap semiconductors. Unlike to BN bilayer, the energy gap of graphene/BN bilayers increases with external field. The magnitude of the change in the band gap of BN bilayers is much higher than the graphene/BN bilayers. Near absolute zero, the σ(T) is zero for BN bilayers and it increases with temperature until reaches maximum value then decreases. The BN/graphene bilayers have larger electrical conductivity larger than BN bilayers. For both bilayers, the specific heat capacity has a Schottky anomaly.

  12. Displacement sensor based on an amorphous bilayer including a magnetostrictive component

    Energy Technology Data Exchange (ETDEWEB)

    Mehnen, L. E-mail: mehnen@gte.tuwien.ac.at; Svec, P.; Pfuetzner, H.; Duhaj, P

    2003-01-01

    The present study concerns a novel type of bilayer material for displacement sensors based on the detection of curvature changes through the magnetoelastic effect. For increased bilayer stability, attempts were made to use a double-nozzle melt spinning technique (DNT) for direct flow-cast of bilayers. Compared to an agglutination technique, DNT yielded much lower sensitivity but improved long-term stability.

  13. Cationic Dimyristoylphosphatidylcholine and Dioleoyloxytrimethylammonium Propane Lipid Bilayers: Atomistic Insight for Structure and Dynamics

    DEFF Research Database (Denmark)

    Zhao, W.; Gurtovenko, A. A.; Vattulainen, I.

    2012-01-01

    of 0.4, that is, at lower TAP fractions compared with saturated PC/TAP bilayers. Adding unsaturated DOTAP lipids into DMPC bilayers was found to promote lipid chain interdigitation and to fluidize lipid bilayers, as seen through enhanced lateral lipid diffusion. The speed-up in lateral diffusion...

  14. Electronic and optical studies of pulse laser deposited ZnO/NiO bilayer film

    Science.gov (United States)

    Baraskar, P.; Dar, T. A.; Choudhary, R. J.; Sen, P. K.; Sen, P.

    2016-10-01

    We report the structural, optical and electronic properties of polycrystalline ZnO and NiO thin films and amorphous ZnO/NiO bilayer film, prepared by pulsed laser deposition technique. Despite of the presence of both Zn and Ni in +2 state in the bilayer film, the grown bilayer shows no reflections (in XRD) corresponding to ZnO or NiO. The difference in crystal structure of ZnO and NiO leads to the strain in the grown bilayer film. An increase in the band gap has been observed in bilayer film which can be attributed to the amorphous nature of the structure.

  15. Efficient tunable generic model for self-assembling fluid bilayer membranes

    Science.gov (United States)

    Deserno, Markus

    2005-03-01

    We present a new model for the simulation of generic lipid bilayers in the mesoscopic regime (between a few nanometers and many tens of nanometers), which is very robust, versatile, and extremely efficient, since it avoids the need for an embedding solvent. Based entirely on simple pair potentials, it features a wide region of unassisted self assembly into fluid bilayers without the need for careful parameter tuning. The resulting membranes display the correct continuum elastic behavior with bending constants in the experimentally relevant range. It can be readily used to study events like bilayer fusion, bilayer melting, lipid mixtures, rafts, and protein-bilayer interactions.

  16. Stable high conductivity ceria/bismuth oxide bilayered electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Wachsman, E.D.; Jayaweera, P.; Jiang, N.; Lowe, D.M.; Pound, B.G. [SRI international, Menlo Park, CA (United States). Materials Research Center

    1997-01-01

    The authors have developed a high conductivity bilayered ceria/bismuth oxide anolyte/electrolyte that uses the Po{sub 2} gradient to obtain stability at the anolyte-electrolyte interface and reduced electronic conduction due to the electrolyte region. Results in terms of solid oxide fuel cell (SOFC) performance and stability are presented. These results include a 90 to 160 mV increase in open-circuit potential, depending on temperature, with the bilayered structure as compared to SOFCs fabricated from a single ceria layer. An open-circuit potential of >1.0 V was obtained at 500 C with the bilayered structure. This increase in open-circuit potential is obtained without any measurable increase in cell resistance and is stable for over 1,400 h of testing, under both open-circuit and maximum power conditions. Moreover, SOFCs fabricated from the bilayered structure result in a 33% greater power density as compared to cells with a single ceria electrolyte layer.

  17. Plasmons in metallic monolayer and bilayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Andersen, Kirsten; Thygesen, Kristian S.

    2013-01-01

    We study the collective electronic excitations in metallic single-layer and bilayer transition metal dichalcogenides (TMDCs) using time dependent density functional theory in the random phase approximation. For very small momentum transfers (below q≈0.02 Å−1), the plasmon dispersion follows the √q...

  18. Super-Sensitive and Robust Biosensors from Supported Polymer Bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Paxton, Walter F. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

    2015-09-01

    Biological organisms are potentially the most sensitive and selective biological detection systems known, yet we are currently severely limited in our ability to exploit biological interactions in sensory devices, due in part to the limited stability of biological systems and derived materials. This proposal addresses an important aspect of integrating biological sensory materials in a solid state device. If successful, such technology could enable entirely new classes of robust biosensors that could be miniaturized and deployed in the field. The critical aims of the proposed work were 1) the calibration of a more versatile approach to measuring pH, 2) the use of this method to monitor pH changes caused by the light-induced pumping of protons across vesicles with bacteriorhodopsin integrated into the membranes (either polymer or lipid); 3) the preparation of bilayer assemblies on platinum surfaces; 4) the enhanced detection of lightinduced pH changes driven by bR-loaded supported bilayers. I have developed a methodology that may enable that at interfaces and developed a methodology to characterize the functionality of bilayer membranes with reconstituted membrane proteins. The integrity of the supported bilayer films however must be optimized prior to the full realization of the work originally envisioned in the original proposal. Nevertheless, the work performed on this project and the encouraging results it has produced has demonstrated that these goals are challenging yet within reach.

  19. Modeling constrained sintering of bi-layered tubular structures

    DEFF Research Database (Denmark)

    Tadesse Molla, Tesfaye; Kothanda Ramachandran, Dhavanesan; Ni, De Wei;

    2015-01-01

    . Furthermore, the model is validated using densification results from sintering of bi-layered tubular ceramic oxygen membrane based on porous MgO and Ce0.9Gd0.1O1.95-d layers. Model input parameters, such as the shrinkage kinetics and viscous parameters are obtained experimentally using optical dilatometry...

  20. Electronic transport of bilayer graphene with asymmetry line defects

    Science.gov (United States)

    Zhao, Xiao-Ming; Wu, Ya-Jie; Chen, Chan; Liang, Ying; Kou, Su-Peng

    2016-11-01

    In this paper, we study the quantum properties of a bilayer graphene with (asymmetry) line defects. The localized states are found around the line defects. Thus, the line defects on one certain layer of the bilayer graphene can lead to an electric transport channel. By adding a bias potential along the direction of the line defects, we calculate the electric conductivity of bilayer graphene with line defects using the Landauer-Büttiker theory, and show that the channel affects the electric conductivity remarkably by comparing the results with those in a perfect bilayer graphene. This one-dimensional line electric channel has the potential to be applied in nanotechnology engineering. Project supported by the National Basic Research Program of China (Grant Nos. 2011CB921803 and 2012CB921704), the National Natural Science Foundation of China (Grant Nos. 11174035, 11474025, 11504285, and 11404090), the Specialized Research Fund for the Doctoral Program of Higher Education, China, the Fundamental Research Funds for the Central Universities, China, the Scientific Research Program Fund of the Shaanxi Provincial Education Department, China (Grant No. 15JK1363), and the Young Talent Fund of University Association for Science and Technology in Shaanxi Province, China.

  1. Forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces.

    Science.gov (United States)

    Zhang, Ying; Wang, Lei; Wang, Xuejing; Qi, Guodong; Han, Xiaojun

    2013-07-01

    A novel method of forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces is introduced. Polyelectrolyte films were fabricated by the layer-by-layer technique on a silicon oxide surface modified with a 3-aminopropyltriethoxysilane (APTES) monolayer. The surface pK(a) value of the APTES monolayer was determined by cyclic voltammetry to be approximately 5.61, on the basis of which a pH value of 2.0 was chosen for layer-by-layer assembly. Micropatterned polyelectrolyte films were obtained by deep-UV (254 nm) photolysis though a mask. Absorbed fluorescent latex beads were used to visualize the patterned surfaces. Lipid bilayer arrays were fabricated on the micropatterned surfaces by immersing the patterned substrates into a solution containing egg phosphatidylcholine vesicles. Fluorescence recovery after photobleaching studies yielded a lateral diffusion coefficient for probe molecules of 1.31±0.17 μm(2) s(-1) in the bilayer region, and migration of the lipid NBD PE in bilayer lipid membrane arrays was observed in an electric field.

  2. Anthrax toxin-induced rupture of artificial lipid bilayer membranes

    Science.gov (United States)

    Nablo, Brian J.; Panchal, Rekha G.; Bavari, Sina; Nguyen, Tam L.; Gussio, Rick; Ribot, Wil; Friedlander, Art; Chabot, Donald; Reiner, Joseph E.; Robertson, Joseph W. F.; Balijepalli, Arvind; Halverson, Kelly M.; Kasianowicz, John J.

    2013-08-01

    We demonstrate experimentally that anthrax toxin complexes rupture artificial lipid bilayer membranes when isolated from the blood of infected animals. When the solution pH is temporally acidified to mimic that process in endosomes, recombinant anthrax toxin forms an irreversibly bound complex, which also destabilizes membranes. The results suggest an alternative mechanism for the translocation of anthrax toxin into the cytoplasm.

  3. Inducing morphological changes in lipid bilayer membranes with microfabricated substrates

    Science.gov (United States)

    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.

  4. Single lipid bilayer deposition on polymer surfaces using bicelles.

    Science.gov (United States)

    Saleem, Qasim; Zhang, Zhenfu; Petretic, Amy; Gradinaru, Claudiu C; Macdonald, Peter M

    2015-03-09

    A lipid bilayer was deposited on a 3 μm diameter polystyrene (PS) bead via hydrophobic anchoring of bicelles containing oxyamine-bearing cholesteric moieties reacting with the aldehyde functionalized bead surface. Discoidal bicelles were formed by mixing dimyristoylphosphatidylcholine (DMPC), dihexanoylphosphatidylcholine (DHPC), dimyristoyltrimethylammonium propane (DMTAP), and the oxyamine-terminated cholesterol derivative, cholest-5-en-3β-oxy-oct-3,6-oxa-an-8-oxyamine (CHOLOA), in the molar ratio DMPC/DHCP/DMTAP/CHOLOA (1/0.5/0.01/0.05) in water. Upon exposure to aldehyde-bearing PS beads, a stable single lipid bilayer coating rapidly formed at the bead surface. Fluorescence recovery after photobleaching demonstrated that the deposited lipids fused into an encapsulating lipid bilayer. Electrospray ionization mass spectrometry showed that the short chain lipid DHPC was entirely absent from the PS adherent lipid coating. Fluorescence quenching measurements proved that the coating was a single lipid bilayer. The bicelle coating method is thus simple and robust, can be modified to include membrane-associated species, and can be adapted to coat any number of different surfaces.

  5. Exchange bias training effect in coupled all ferromagnetic bilayer structures

    Science.gov (United States)

    Polisetty, Srinivas; He, Xi; Binek, Christian; Berger, Andreas

    2006-03-01

    We study exchange coupled bilayers of soft and hard ferromagnetic (FM) thin films by means of Alternating Gradient Force Magnetometry. A CoCr thin film realizes the magnetically soft layer (SL) which is exchange coupled via a Ru-interlayer with a hard CoPtCrB pinning layer (HL). This new class of all FM bilayers shows remarkable analogies to conventional antiferromagnetic (AF)/FM exchange bias (EB) heterostructures. Not only do these all FM bilayers exhibit a tunable EB effect, they also show a distinct training behavior upon cycling the SL through consecutive hysteresis loops. Training resembles the cycle dependent evolution of the bias field and is to a large extend analogous to the gradual degradation of the EB field observed upon cycling the FM top layer of a AF/FM EB heterostructure through consecutive hysteresis loops. However, in contrast to these conventional EB systems, our all FM bilayer structures allow the observation of training induced changes in the bias-setting HL by means of simple magnetometry. Our experiments show unambiguously that the training effect is driven by deviations from equilibrium in the pinning layer. A comparison of the experimental data with predictions from a theory based upon triggered relaxation phenomena shows excellent agreement.

  6. The lipid bilayer membrane and its interactions with additives

    NARCIS (Netherlands)

    Meijer, L.A.

    1994-01-01

    The aim of this study was to make accurate predictions on the interaction of biologically relevant molecules with lipid bilayer membranes. We emphasised on the partitioning of these molecules between the membrane phase, and the aqueous phase quantified by the partition coefficient. To make

  7. Berry phase and pseudospin winding number in bilayer graphene

    Science.gov (United States)

    Park, Cheol-Hwan; Marzari, Nicola

    2012-02-01

    In 2006, two seminal studies on the novel quantum Hall effect of bilayer graphene [K. S. Novoselov et al., Nat. Phys. 2, 177 (2006); E. McCann and V. I. Fal'ko, Phys. Rev. Lett. 96, 086805 (2006)] appeared. Those papers claim that a non-trivial Berry phase of 2π in bilayer graphene is responsible for the novel quantum Hall effect described. Since then, it has become widely accepted by people working on the novel physics of graphene nanostructures that bilayer graphene has a non-trivial Berry phase of 2π (different from 0, as for conventional two-dimensional electron gas). In this talk, we show that (i) the relevant Berry phase for bilayer graphene is the same as that for a conventional two-dimensional electron gas and especially that (ii) what is actually obtained in the quantum Hall measurements is not the absolute value of the Berry phase of graphene multilayers but the pseudospin winding number. The results of our study ask for a re-interpretation of the numerous works related to the Berry phase in graphene multilayers.

  8. Supported lipid bilayers with controlled curvature via colloidal lithography

    DEFF Research Database (Denmark)

    Sundh, Maria; Manandhar, Michal; Svedhem, Sofia

    2011-01-01

    Supported lipid bilayers (SLBs) at surfaces provide a route to quantitatively study molecular interactions with and at lipid membranes via different surface-based analytical techniques. Here, a method to fabricate SLBs with controlled curvatures, in the nanometer regime over large areas, is prese...

  9. The lipid bilayer membrane and its interactions with additives.

    NARCIS (Netherlands)

    Meijer, L.A.

    1994-01-01

    The aim of this study was to make accurate predictions on the interaction of biologically relevant molecules with lipid bilayer membranes. We emphasised on the partitioning of these molecules between the membrane phase, and the aqueous phase quantified by the partition coefficient. To make detailed

  10. Dynamic combinatorial chemistry at the phospholipid bilayer interface

    NARCIS (Netherlands)

    Mansfeld, Friederike M.; Au-Yeung, Ho Yu; Sanders, Jeremy K.M.; Otto, Sijbren

    2010-01-01

    Background: Molecular recognition at the environment provided by the phospholipid bilayer interface plays an important role in biology and is subject of intense investigation. Dynamic combinatorial chemistry is a powerful approach for exploring molecular recognition, but has thus far not been

  11. Indole Localization in an Explicit Bilayer Revealed via Molecular Dynamics

    Science.gov (United States)

    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.

  12. Effects of imidazolium-based ionic surfactants on the size and dynamics of phosphatidylcholine bilayers with saturated and unsaturated chains.

    Science.gov (United States)

    Lee, Hwankyu

    2015-07-01

    Imidazolium-based ionic surfactants of different sizes were simulated with 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayers. Regardless of the phospholipid type, larger surfactants at higher concentrations more significantly insert into the bilayer and increase the bilayer-surface size, in agreement with experiments and previous simulations. Insertion of surfactants only slightly decreases the bilayer thickness, as also observed in experiments. Although the surfactant insertion and its effect on the bilayer size and thickness are similar in different types of bilayers, the volume fractions of surfactants in the bilayer are higher for DMPC bilayers than for POPC and DOPC bilayers. In particular, ionic surfactants with four hydrocarbons yield their volume fractions of 4.6% and 8.7%, respectively, in POPC and DMPC bilayers, in quantitative agreement with experimental values of ∼5% and ∼10%. Also, the inserted surfactants increase the lateral diffusivity of the bilayer, which depends on the bilayer type. These findings indicate that although the surfactant insertion does not depend on the bilayer type, the effects of surfactants on the volume fraction and bilayer dynamics occur more significantly in the DMPC bilayer because of the smaller area per lipid and shorter saturated tails, which helps explain the experimental observations regarding different volume fractions of surfactants in POPC and DMPC bilayers.

  13. Cholesterol enhances surface water diffusion of phospholipid bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Chi-Yuan; Kausik, Ravinath; Han, Songi, E-mail: songi@chem.ucsb.edu [Department of Chemistry and Biochemistry and Materials Research Laboratory, University of California, Santa Barbara, California 93106 (United States); Olijve, Luuk L. C. [Laboratory of Macromolecular and Organic Chemistry and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven (Netherlands)

    2014-12-14

    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 headgroups 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

  14. Evaporation-Induced Buckling and Fission of Microscale Droplet Interface Bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Boreyko, Jonathan B [ORNL; Mruetusatorn, Prachya [ORNL; Sarles, Stephen A [ORNL; Retterer, Scott T [ORNL; Collier, Pat [ORNL

    2013-01-01

    Droplet interface bilayers (DIBs) are a robust platform for studying synthetic cellular membranes; however, to date no DIBs have been produced at cellular length scales. Here, we create microscale droplet interface bilayers ( DIBs) at the interface between aqueous femtoliter-volume droplets within an oil-filled microfluidic channel. The uniquely large area-to-volume ratio of the droplets results in strong evaporation effects, causing the system to transition through three distinct regimes. First, the two adjacent droplets shrink into the shape of a single spherical droplet, where an augmented lipid bilayer partitions two hemi-spherical volumes. In the second regime, the combined effects of the shrinking monolayers and growing bilayer force the confined bilayer to buckle to conserve its mass. Finally, at a bending moment corresponding to a critical shear stress, the buckling bilayer fissions a vesicle to regulate its shape and stress. The DIBs produced here enable evaporation-induced bilayer dynamics reminiscent of endo- and exocytosis in cells.

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

    Science.gov (United States)

    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.

  16. Evaluation of the performance characteristics of bilayer tablets: Part II. Impact of environmental conditions on the strength of bilayer tablets.

    Science.gov (United States)

    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.

  17. VISUALIZATION AND ANALYSIS OF LPS DISTRIBUTION IN BINARY PHOSPHOLIPID BILAYERS

    Science.gov (United States)

    Florencia, Henning María; Susana, Sanchez; Laura, Bakás

    2010-01-01

    Lipopolysaccharide (LPS) is an endotoxin released from the outer membrane of Gram negative bacteria during infections. It have been reported that LPS may play a rol in the outer membrane of bacteria similar to that of cholesterol in eukaryotic plasma membranes. In this article we compare the effect of introducing LPS or cholesterol in liposomes made of dipalmitoylphosphatidylcholine/dioleoylphosphatidylcholine on the solubilization process by Triton X-100. The results show that liposomes containing LPS or Cholesterol are more resistant to solubilization by Triton X-100 than the binary phospholipid mixtures at 4°C. The LPS distribution was analyzed on GUVs of DPPC:DOPC using FITC-LPS. Solid and liquid-crystalline domains were visualized labeling the GUVs with LAURDAN and GP images were acquired using a two-photon microscope. The images show a selective distribution of LPS in gel domains. Our results support the hypothesis that LPS could aggregate and concentrate selectively in biological membranes providing a mechanism to bring together several components of the LPS-sensing machinery. PMID:19324006

  18. Visualization and analysis of lipopolysaccharide distribution in binary phospholipid bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Henning, Maria Florencia [Instituto de Investigaciones Bioquimicas La Plata (INIBIOLP), CCT-La Plata, CONICET, Facultad de Ciencias Medicas, UNLP, Calles 60 y 120, 1900 La Plata (Argentina); Sanchez, Susana [Laboratory for Fluorescence Dynamics, University of California-Irvine, Irvine, CA (United States); Bakas, Laura, E-mail: lbakas@biol.unlp.edu.ar [Instituto de Investigaciones Bioquimicas La Plata (INIBIOLP), CCT-La Plata, CONICET, Facultad de Ciencias Medicas, UNLP, Calles 60 y 120, 1900 La Plata (Argentina); Departamento de Ciencias Biologicas, Facultad de Ciencias Exactas, UNLP, Calles 47 y 115, 1900 La Plata (Argentina)

    2009-05-22

    Lipopolysaccharide (LPS) is an endotoxin released from the outer membrane of Gram-negative bacteria during infections. It have been reported that LPS may play a role in the outer membrane of bacteria similar to that of cholesterol in eukaryotic plasma membranes. In this article we compare the effect of introducing LPS or cholesterol in liposomes made of dipalmitoylphosphatidylcholine/dioleoylphosphatidylcholine on the solubilization process by Triton X-100. The results show that liposomes containing LPS or cholesterol are more resistant to solubilization by Triton X-100 than the binary phospholipid mixtures at 4 {sup o}C. The LPS distribution was analyzed on GUVs of DPPC:DOPC using FITC-LPS. Solid and liquid-crystalline domains were visualized labeling the GUVs with LAURDAN and GP images were acquired using a two-photon microscope. The images show a selective distribution of LPS in gel domains. Our results support the hypothesis that LPS could aggregate and concentrate selectively in biological membranes providing a mechanism to bring together several components of the LPS-sensing machinery.

  19. Aqueous solutions at the interface with phospholipid bilayers.

    Science.gov (United States)

    Berkowitz, Max L; Vácha, Robert

    2012-01-17

    In a sense, life is defined by membranes, because they delineate the barrier between the living cell and its surroundings. Membranes are also essential for regulating the machinery of life throughout many interfaces within the cell's interior. A large number of experimental, computational, and theoretical studies have demonstrated how the properties of water and ionic aqueous solutions change due to the vicinity of membranes and, in turn, how the properties of membranes depend on the presence of aqueous solutions. Consequently, understanding the character of aqueous solutions at their interface with biological membranes is critical to research progress on many fronts. The importance of incorporating a molecular-level description of water into the study of biomembrane surfaces was demonstrated by an examination of the interaction between phospholipid bilayers that can serve as model biological membranes. The results showed that, in addition to well-known forces, such as van der Waals and screened Coulomb, one has to consider a repulsion force due to the removal of water between surfaces. It was also known that physicochemical properties of biological membranes are strongly influenced by the specific character of the ions in the surrounding aqueous solutions because of the observation that different anions produce different effects on muscle twitch tension. In this Account, we describe the interaction of pure water, and also of aqueous ionic solutions, with model membranes. We show that a symbiosis of experimental and computational work over the past few years has resulted in substantial progress in the field. We now better understand the origin of the hydration force, the structural properties of water at the interface with phospholipid bilayers, and the influence of phospholipid headgroups on the dynamics of water. We also improved our knowledge of the ion-specific effect, which is observed at the interface of the phospholipid bilayer and aqueous solution, and its

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

    Science.gov (United States)

    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

  1. The Mechanical Aspects of Formation and Application of PDMS Bilayers Rolled into a Cylindrical Structure

    Directory of Open Access Journals (Sweden)

    Dongwon Kang

    2015-01-01

    Full Text Available A polydimethylsiloxane (PDMS film with its surface being oxidized by a plasma treatment or a UV-ozone (UVO treatment, that is, a bilayer made of PDMS and its oxidized surface layer, is known to roll into a cylindrical structure upon exposure to the chloroform vapor due to the mismatch in the swelling ratio between PDMS and the oxidized layer by the chloroform vapor. Here we analyzed the formation of the rolled bilayer with the mechanical aspects: how the mismatch in the swelling ratio of the bilayer induces rolling of the bilayer, why any form of trigger that breaks the symmetry in the in-plane stress level is needed to roll the bilayer uniaxially, why the rolled bilayer does not unroll in the dry state when there is no more mismatch in the swelling ratio, and how the measured curvature of rolled bilayer matches well with the prediction by the theory. Moreover, for the use of the rolled bilayer as the channel of the microfluidic device, we examined whether the rolled bilayer deforms or unrolls by the flow of the aqueous solution that exerts the circumferential stress on the rolled bilayer.

  2. A Molecular Dynamics Study of the Structural and Dynamical Properties of Putative Arsenic Substituted Lipid Bilayers

    Directory of Open Access Journals (Sweden)

    Ratna Juwita

    2013-04-01

    Full Text Available Cell membranes are composed mainly of phospholipids which are in turn, composed of five major chemical elements: carbon, hydrogen, nitrogen, oxygen, and phosphorus. Recent studies have suggested the possibility of sustaining life if the phosphorus is substituted by arsenic. Although this issue is still controversial, it is of interest to investigate the properties of arsenated-lipid bilayers to evaluate this possibility. In this study, we simulated arsenated-lipid, 1-palmitoyl-2-oleoyl-sn-glycero-3-arsenocholine (POAC, lipid bilayers using all-atom molecular dynamics to understand basic structural and dynamical properties, in particular, the differences from analogous 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, (POPC lipid bilayers. Our simulations showed that POAC lipid bilayers have distinct structural and dynamical properties from those of native POPC lipid bilayers. Relative to POPC lipid bilayers, POAC lipid bilayers have a more compact structure with smaller lateral areas and greater order. The compact structure of POAC lipid bilayers is due to the fact that more inter-lipid salt bridges are formed with arsenate-choline compared to the phosphate-choline of POPC lipid bilayers. These inter-lipid salt bridges bind POAC lipids together and also slow down the head group rotation and lateral diffusion of POAC lipids. Thus, it would be anticipated that POAC and POPC lipid bilayers would have different biological implications.

  3. A large scale molecular dynamics calculation of a lipid bilayer

    Energy Technology Data Exchange (ETDEWEB)

    Okazaki, Susumu [Tokyo Inst. of Tech. (Japan)

    1998-03-01

    Long time molecular dynamics simulations for the dipalmitoylphosphatidylcholine lipid bilayer in the liquid crystal phase could successfully be performed in the isothermal-isobaric ensemble using the Nose-Parrinello-Rahman extended system method. Three independent 2 ns calculations show excellent convergence to the same equilibrium state of the system in about 0.5 ns. Various structural properties such a atomic distribution, order parameter, gauche fraction in the alkyl chains, and bent structure of the head group and sn-2 chain were satisfactorily reproduced. Dynamic quantities such as trans-gauche transition were qualitatively in good correspondence the experiment. The calculations presented a microscopic picture of the whole molecular conformations, including the finding that there is not a collective tilt in bilayer. Some interesting dynamical observations concerning large structural fluctuations and pendulum motion of the alkyl chains were also made. (author)

  4. Formation of droplet interface bilayers in a Teflon tube

    Science.gov (United States)

    Walsh, Edmond; Feuerborn, Alexander; Cook, Peter R.

    2016-09-01

    Droplet-interface bilayers (DIBs) have applications in disciplines ranging from biology to computing. We present a method for forming them manually using a Teflon tube attached to a syringe pump; this method is simple enough it should be accessible to those without expertise in microfluidics. It exploits the properties of interfaces between three immiscible liquids, and uses fluid flow through the tube to pack together drops coated with lipid monolayers to create bilayers at points of contact. It is used to create functional nanopores in DIBs composed of phosphocholine using the protein α-hemolysin (αHL), to demonstrate osmotically-driven mass transfer of fluid across surfactant-based DIBs, and to create arrays of DIBs. The approach is scalable, and thousands of DIBs can be prepared using a robot in one hour; therefore, it is feasible to use it for high throughput applications.

  5. Formation of droplet interface bilayers in a Teflon tube.

    Science.gov (United States)

    Walsh, Edmond; Feuerborn, Alexander; Cook, Peter R

    2016-09-29

    Droplet-interface bilayers (DIBs) have applications in disciplines ranging from biology to computing. We present a method for forming them manually using a Teflon tube attached to a syringe pump; this method is simple enough it should be accessible to those without expertise in microfluidics. It exploits the properties of interfaces between three immiscible liquids, and uses fluid flow through the tube to pack together drops coated with lipid monolayers to create bilayers at points of contact. It is used to create functional nanopores in DIBs composed of phosphocholine using the protein α-hemolysin (αHL), to demonstrate osmotically-driven mass transfer of fluid across surfactant-based DIBs, and to create arrays of DIBs. The approach is scalable, and thousands of DIBs can be prepared using a robot in one hour; therefore, it is feasible to use it for high throughput applications.

  6. Formation of droplet interface bilayers in a Teflon tube

    Science.gov (United States)

    Walsh, Edmond; Feuerborn, Alexander; Cook, Peter R.

    2016-01-01

    Droplet-interface bilayers (DIBs) have applications in disciplines ranging from biology to computing. We present a method for forming them manually using a Teflon tube attached to a syringe pump; this method is simple enough it should be accessible to those without expertise in microfluidics. It exploits the properties of interfaces between three immiscible liquids, and uses fluid flow through the tube to pack together drops coated with lipid monolayers to create bilayers at points of contact. It is used to create functional nanopores in DIBs composed of phosphocholine using the protein α-hemolysin (αHL), to demonstrate osmotically-driven mass transfer of fluid across surfactant-based DIBs, and to create arrays of DIBs. The approach is scalable, and thousands of DIBs can be prepared using a robot in one hour; therefore, it is feasible to use it for high throughput applications. PMID:27681313

  7. First-principles modeling hydrogenation of bilayered boron nitride

    Science.gov (United States)

    Jing, Wang; Peng, Zhang; Xiang-Mei, Duan

    2016-05-01

    We have investigated the structural and electronic characteristics of hydrogenated boron-nitride bilayer (H-BNBN-H) using first-principles calculations. The results show that hydrogenation can significantly reduce the energy gap of the BN-BN into the visible-light region. Interestingly, the electric field induced by the interface dipoles helps to promote the formation of well-separated electron-hole pairs, as demonstrated by the charge distribution of the VBM and CBM. Moreover, the applied bias voltage on the vertical direction of the bilayer could modulate the band gap, resulting in transition from semiconductor to metal. We conclude that H-BNBN-H could improve the solar energy conversion efficiency, which may provide a new way for tuning the electronic devices to meet different environments and demands. Project supported by the National Natural Science Foundation of China (Grant No. 11574167).

  8. Bilayer graphene: physics and application outlook in photonics

    Directory of Open Access Journals (Sweden)

    Yan Hugen

    2015-05-01

    Full Text Available Layered materials, such as graphene, transition metal dichacogenides and black phosphorus have attracted lots of attention recently. They are emerging novel materials in electronics and photonics, with tremendous potential in revolutionizing the traditional electronics and photonics industry. Marrying layered material to the nanophotonics is being proved fruitful. With the recent emphasis and development of metasurfaces in nanophotonics, atomically thin materials can find their unique position and strength in this field. In this article, I will focus on one specific two dimensional material: bilayer graphene. Basic physics will be reviewed, such as band-gap opening, electron-phonon interaction, phonon-plasmon interaction and Fano resonances in the optical response. Moreover, I will review the application of bilayer graphene as a sensitive and fast photodetector. An outlook will be given in the final part of the paper.

  9. Elliptical structure of phospholipid bilayer nanodiscs encapsulated by scaffold proteins

    DEFF Research Database (Denmark)

    Skar-Gislinge, Nicholas; Simonsen, Jens Bæk; Mortensen, Kell

    2010-01-01

    -angle neutron scattering in combination with variable-temperature studies of synchrotron small-angle X-ray scattering on nanodiscs in solution, we show that the fundamental nanodisc unit, consisting of a lipid bilayer surrounded by amphiphilic scaffold proteins, possesses intrinsically an elliptical shape....... The temperature dependence of the curvature of the nanodiscs prepared with two different phospholipid types (DLPC and POPC) shows that it is the scaffold protein that determines the overall elliptical shape and that the nanodiscs become more circular with increasing temperature. Our data also show...... that the hydrophobic bilayer thickness is, to a large extent, dictated by the scaffolding protein and adjusted to minimize the hydrophobic mismatch between protein and phospholipid. Our conclusions result from a new comprehensive and molecular-based model of the nanodisc structure and the use of this to analyze...

  10. Phase-separation transitions in asymmetric lipid bilayers

    CERN Document Server

    Shimobayashi, Shunsuke F; Taniguchi, Takashi

    2015-01-01

    Morphological transitions of phase separation associated with the asymmetry of lipid composition were investigated using micrometer-sized vesicles of lipid bilayers made from a lipid mixture. The complete macro-phase-separated morphology undergoes a transition to a micro-phase-separation-like morphology via a lorate morphology as a metastable state. The transition leads to the emergence of monodisperse nanosized domains through repeated domain scission events. Moreover, we have numerically confirmed the transitions using the time-dependent Ginzburg-Landau model describing phase separation and the bending elastic membrane, which is quantitatively consistent with experimental results by fixing one free parameter. Our findings suggest that the local spontaneous curvature due to the asymmetric composition plays an essential role in the thermodynamic stabilization of micro-phase separation in lipid bilayers.

  11. One-dimensional topological edge states of bismuth bilayers

    Science.gov (United States)

    Drozdov, Ilya K.; Alexandradinata, A.; Jeon, Sangjun; Nadj-Perge, Stevan; Ji, Huiwen; Cava, R. J.; Andrei Bernevig, B.; Yazdani, Ali

    2014-09-01

    The hallmark of a topologically insulating state of matter in two dimensions protected by time-reversal symmetry is the existence of chiral edge modes propagating along the perimeter of the sample. Among the first systems predicted to be a two-dimensional topological insulator are bilayers of bismuth. Here we report scanning tunnelling microscopy experiments on bulk Bi crystals that show that a subset of the predicted Bi-bilayers' edge states are decoupled from the states of the substrate and provide direct spectroscopic evidence of their one-dimensional nature. Moreover, by visualizing the quantum interference of edge-mode quasi-particles in confined geometries, we demonstrate their remarkable coherent propagation along the edge with scattering properties consistent with strong suppression of backscattering as predicted for the propagating topological edge states.

  12. Model for magnetostrictive performance in soft/hard coupled bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Jianjun, Li, E-mail: ljj8081@gmail.com [National Key Laboratory of Science and Technology on Advanced Composites in Special Environments, Harbin Institute of Technology, Harbin 150080 (China); Laboratoire de Magnétisme de Bretagne, Université de Bretagne Occidentale, 29238 Brest Cedex 3 (France); Beibei, Duan; Minglun, Li [National Key Laboratory of Science and Technology on Advanced Composites in Special Environments, Harbin Institute of Technology, Harbin 150080 (China)

    2015-11-01

    A model is set up to investigate the magnetostrictive performance and spin response in soft/hard magnetostrictive coupled bilayers. Direct coupling between soft ferromagnet and hard TbFe{sub 2} at the interface is assumed. The magnetostriction results from the rotation of ferromagnetic vector and TbFe{sub 2} vectors from the easy axis driven by applied magnetic field. Dependence of magnetostriction on TbFe{sub 2} layer thickness and interfacial exchange interaction is studied. The simulated results reveal the compromise between interfacial exchange interaction and anisotropy of TbFe{sub 2} hard layer. - Highlights: • A model for magnetostrictive performance in soft/hard coupled bilayers. • Simulated magnetostriction loop and corresponding spin response. • Competition and compromise between interfacial interaction and TbFe{sub 2} anisotropy. • Dependence of saturated magnetostriction on different parameters.

  13. Bilayer thickness mismatch controls domain size in biomimetic membranes

    Science.gov (United States)

    Heberle, Frederick A.; Petruzielo, Robin S.; Pan, Jianjun; Drazba, Paul; Kučerka, Norbert; Standaert, Robert F.; Feigenson, Gerald W.; Katsara, John

    2013-03-01

    In order to promote functionality, cells may alter the spatial organization of membrane lipids and proteins, including separation of liquid phases into distinct domains. In model membranes, domain size and morphology depend strongly on composition and temperature, but the physicochemical mechanisms controlling them are poorly understood. Theoretical work suggests a role for interfacial energy at domain boundaries, which may be driven in part by thickness mismatch between a domain and its surrounding bilayer. However, no direct evidence linking thickness mismatch to domain size in free-standing bilayers has been reported. We describe the use of Small Angle Neutron Scattering (SANS) to detect domains in simplified lipid-only models that mimic the composition of plasma membrane. We find that domain size is controlled by the degree of acyl chain unsaturation of low-melting temperature lipids, and that this size transition is correlated to changes in the thickness mismatch between coexisting liquid phases.

  14. Asymmetric bilayer graphene nanoribbon MOSFETs for analog and digital electronics

    Science.gov (United States)

    Dinarvand, A.; Ahmadi, V.; Darvish, Gh.

    2016-05-01

    In this paper, a new structure was proposed for bilayer graphene nanoribbon field-effect transistor (BGNFET) mainly to enhance the electrical characteristics in analog and digital applications. The proposed device uses two metallic gates on the top and bottom of a bilayer graphene nanoribbon, which is surrounded by SiO2 and connected to heavily doped source/drain contacts. Electrical properties of the proposed device were explored using fully self-consistent solution of Poisson and Schrödinger equations based on the nonequilibrium Green's function (NEGF) formalism. Significant improvements in the electrical behavior was seen in the simulation results for gates asymmetrically biased. The comparison with graphene nanoribbon FET showed that the proposed structure benefited from higher intrinsic voltage gain and cut-off frequency and improved switching characteristics such as delay and Ion/Ioff ratio.

  15. Dipolar bilayer with antiparallel polarization: A self-bound liquid

    Science.gov (United States)

    Hebenstreit, Martin; Rader, Michael; Zillich, Robert E.

    2016-01-01

    Dipolar bilayers with antiparallel polarization, i.e., opposite polarization in the two layers, exhibit liquidlike rather than gaslike behavior. In particular, even without external pressure, a self-bound liquid droplet of constant density will form. We investigate the symmetric case of two identical layers, corresponding to a two-component Bose system with equal partial densities. The zero-temperature equation of state E (ρ )/N , where ρ is the total density, has a minimum, with an equilibrium density that can be adjusted by the distance d between the layers (decreasing with increasing d ). The attraction necessary for a self-bound liquid comes from the interlayer dipole-dipole interaction that leads to a mediated intralayer attraction. We investigate the regime of negative pressure towards the spinodal instability, where the bilayer is unstable against infinitesimal fluctuations of the total density, confirmed by calculations of the speed of sound of total density fluctuations.

  16. Polyglutamine expansion in huntingtin increases its insertion into lipid bilayers.

    Science.gov (United States)

    Kegel, Kimberly B; Schewkunow, Vitali; Sapp, Ellen; Masso, Nicholas; Wanker, Erich E; DiFiglia, Marian; Goldmann, Wolfgang H

    2009-09-25

    An expanded polyglutamine (Q) tract (>37Q) in huntingtin (htt) causes Huntington disease. Htt associates with membranes and polyglutamine expansion in htt may alter membrane function in Huntington disease through a mechanism that is not known. Here we used differential scanning calorimetry to examine the effects of polyQ expansion in htt on its insertion into lipid bilayers. We prepared synthetic lipid vesicles composed of phosphatidylcholine and phosphatidylethanolamine and tested interactions of htt amino acids 1-89 with 20Q, 32Q or 53Q with the vesicles. GST-htt1-89 with 53Q inserted into synthetic lipid vesicles significantly more than GST-htt1-89 with 20Q or 32Q. We speculate that by inserting more into cell membranes, mutant huntingtin could increase disorder within the lipid bilayer and thereby disturb cellular membrane function.

  17. Bilayer Thickness Mismatch Controls Domain Size in Model Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Heberle, Frederick A [ORNL; Petruzielo, Robin S [ORNL; Pan, Jianjun [ORNL; Drazba, Paul [ORNL; Kucerka, Norbert [Canadian Neutron Beam Centre and Comelius University (Slovakia); Feigenson, Gerald [Cornell University; Katsaras, John [ORNL

    2013-01-01

    The observation of lateral phase separation in lipid bilayers has received considerable attention, especially in connection to lipid raft phenomena in cells. It is widely accepted that rafts play a central role in cellular processes, notably signal transduction. While micrometer-sized domains are observed with some model membrane mixtures, rafts much smaller than 100 nm beyond the reach of optical microscopy are now thought to exist, both in vitro and in vivo. We have used small-angle neutron scattering, a probe free technique, to measure the size of nanoscopic membrane domains in unilamellar vesicles with unprecedented accuracy. These experiments were performed using a four-component model system containing fixed proportions of cholesterol and the saturated phospholipid 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC), mixed with varying amounts of the unsaturated phospholipids 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1,2-dioleoylsn- glycero-3-phosphocholine (DOPC). We find that liquid domain size increases with the extent of acyl chain unsaturation (DOPC:POPC ratio). Furthermore, we find a direct correlation between domain size and the mismatch in bilayer thickness of the coexisting liquid-ordered and liquid-disordered phases, suggesting a dominant role for line tension in controlling domain size. While this result is expected from line tension theories, we provide the first experimental verification in free-floating bilayers. Importantly, we also find that changes in bilayer thickness, which accompany changes in the degree of lipid chain unsaturation, are entirely confined to the disordered phase. Together, these results suggest how the size of functional domains in homeothermic cells may be regulated through changes in lipid composition.

  18. Comment on "Raman spectra of misoriented bilayer graphene"

    OpenAIRE

    Ni, Zhenhua; Wang, Yingying; Yu, Ting; You, Yumeng; Shen, Zexiang

    2009-01-01

    In a recent paper [Phys. Rev. B 78, 113407 (2008)], Poncharal et al. studied the Raman spectra of misoriented bilayer graphene. They found that the blueshift of 2D band of misoriented graphene relative to that of single layer graphene shows a strong dependence on the excitation laser energy. The blueshift increases with decreasing excitation energy. This finding contradicts our explanation of reduction of Fermi velocity of folded/misoriented graphene [Ni et al. Phys. Rev. B 77, 235403 (2008)]...

  19. Bending elastic moduli of lipid bilayers : modulation by solutes

    OpenAIRE

    Duwe, H.P.; Kaes, J.; Sackmann, E.

    1990-01-01

    We present high precision measurements of the bending elastic moduli for bilayers of a variety of different lipids and of modifications of the flexural rigidity by solutes. The measurements are based on the Fourier analysis of thermally excited membrane undulations (vesicle shape fluctuations) using a recently developed dynamic image processing method. Measurements of the bending modulus as a function of the undulation wave vector provide information on the limitation of the excitations by th...

  20. Optimizing non-Pb radiation shielding materials using bilayers

    Energy Technology Data Exchange (ETDEWEB)

    McCaffrey, J. P.; Mainegra-Hing, E.; Shen, H. [Institute for National Measurement Standards, National Research Council of Canada, Building M-35, 1200 Montreal Road, Ottawa K1A 0R6 (Canada)

    2009-12-15

    Purpose: The objective of this study was to demonstrate that the weight of non-Pb radiation shielding materials can be minimized by structuring the material as a bilayer composed of different metal-powder-embedded elastomer layers. Methods: Measurements and Monte Carlo (MC) calculations were performed to study the attenuation properties of several non-Pb metal bilayers over the x-ray energy range 30-150 keV. Metals for the layers were chosen on the basis of low cost, nontoxicity, and complementary photoelectric absorption characteristics. The EGSnrc user code cavity.cpp was used to calculate the resultant x-ray fluence spectra after attenuation by these metal layers. Air kerma attenuation was measured using commercially manufactured metal/elastomer test layers. These layers were irradiated using the primary standard calibration beams at the Institute for National Measurement Standards in Ottawa, Canada utilizing the six x-ray beam qualities recommended in the German Standard DIN 6857. Both the measurements and the calculations were designed to approximate surface irradiation as well as penetrating radiation at 10 mm depth in soft tissue. The MC modeling point and the position of the measurement detector for surface irradiation were both directly against the downstream face of the attenuating material, as recommended in DIN 6857. Results: The low-Z upstream/high-Z downstream ordering of the metal bilayers provided substantially more attenuation than the reverse order. Optimal percentages of each metal in each bilayer were determined for each x-ray radiation beam quality. Conclusions: Depending on the x-ray quality, appropriate choices of two complementary metal-embedded elastomer layers can decrease the weight of radiation shielding garments by up to 25% compared to Pb-based elastomer garments while providing equivalent attenuation.

  1. Molecular doping and band-gap opening of bilayer graphene.

    Science.gov (United States)

    Samuels, Alexander J; Carey, J David

    2013-03-26

    The ability to induce an energy band gap in bilayer graphene is an important development in graphene science and opens up potential applications in electronics and photonics. Here we report the emergence of permanent electronic and optical band gaps in bilayer graphene upon adsorption of π electron containing molecules. Adsorption of n- or p-type dopant molecules on one layer results in an asymmetric charge distribution between the top and bottom layers and in the formation of an energy gap. The resultant band gap scales linearly with induced carrier density though a slight asymmetry is found between n-type dopants, where the band gap varies as 47 meV/10(13) cm(-2), and p-type dopants where it varies as 40 meV/10(13) cm(-2). Decamethylcobaltocene (DMC, n-type) and 3,6-difluoro-2,5,7,7,8,8-hexacyano-quinodimethane (F2-HCNQ, p-type) are found to be the best molecules at inducing the largest electronic band gaps up to 0.15 eV. Optical adsorption transitions in the 2.8-4 μm region of the spectrum can result between states that are not Pauli blocked. Comparison is made between the band gaps calculated from adsorbate-induced electric fields and from average displacement fields found in dual gate bilayer graphene devices. A key advantage of using molecular adsorption with π electron containing molecules is that the high binding energy can induce a permanent band gap and open up possible uses of bilayer graphene in mid-infrared photonic or electronic device applications.

  2. Self-assembling bilayers of palladiumthiolates in organic media

    Indian Academy of Sciences (India)

    P John Thomas; A Lavanya; V Sabareesh; G U Kulkarni

    2001-10-01

    Alkylthiolates of palladium forming a homologous series (butyl to octadecyl) have been prepared and characterized using X-ray diffraction and STM. The thiolates adopt an unusual bilayered lamellar structure, whose thickness is governed by the length of the alkyl chain. These mesophases melt in the temperature range, 60° to 100°C, with the melting point increasing linearly with the thiol chain length. There is evidence to suggest that the alkyl chains are orientationally disordered especially prior to melting.

  3. Reversal of exchange bias in nanocrystalline antiferromagnetic-ferromagnetic bilayers

    CERN Document Server

    Prados, C; Hernando, A; Montone, A

    2002-01-01

    The sign of the exchange bias in field cooled nanocrystalline antiferromagnetic-ferromagnetic bilayers (Co-O and Ni-O/permalloy) is reversed at temperatures approaching the antiferromagnetic (AFM) blocking temperature. A similar phenomenon is observed after magnetic training processes at similar temperatures. These effects can be explained assuming that the boundaries of nanocrystalline grains in AFM layers exhibit lower transition temperatures than grain cores.

  4. Pedot and PPy Conducting Polymer Bilayer and Trilayer Actuators

    DEFF Research Database (Denmark)

    Zainudeen, Umer Lebbe; Careem, Mohamed Abdul; Skaarup, Steen

    2008-01-01

    Actuators based on conducting polymers are attracting increasing interest due to their desirable features such as large mechanical stress generated, sufficient maximum strain values, high reversibility, good safety properties and the possibility of precise control using small voltages. Many...... attempts have been made to improve the actuator performance. We report electromechanical measurements on actuators of bilayer and trilayer free standing films prepared with polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymers. Both types of conducting polymer are pre...

  5. Coherence and Optical Emission from Bilayer Exciton Condensates

    Directory of Open Access Journals (Sweden)

    D. W. Snoke

    2011-01-01

    Full Text Available Experiments aimed at demonstrating Bose-Einstein condensation of excitons in two types of experiments with bilayer structures (coupled quantum wells are reviewed, with an emphasis on the basic effects. Bose-Einstein condensation implies the existence of a macroscopic coherence, also known as off-diagonal long-range order, and proposed tests and past claims for coherence in these excitonic systems are discussed.

  6. A defect mediated lamellar to isotropic transition of amphiphile bilayers

    OpenAIRE

    Pal, Antara; Pabst, Georg; Raghunathan, V. A.

    2011-01-01

    We report the observation of a novel isotropic phase of amphiphile bilayers in a mixed system consisting of the ionic surfactant, sodium docecylsulphate (SDS), and the organic salt p-toludine hydrochloride (PTHC). This system forms a collapsed lamellar ($L_\\alpha$) phase over a wide range of water content, which transforms into an isotropic phase on heating. This transition is not observed in samples without excess water, where the $L_\\alpha$ phase is stable at higher temperatures. Our observ...

  7. Electronic confinement and ordering instabilities in colossal magnetoresistive bilayer manganites.

    NARCIS (Netherlands)

    Trinckauf, J.; Hanke, T.; Zabolotnyy, V.; Ritschel, T.; Apostu, M.O.; Suryanarayanan, R.; Revcolevschi, A.; Koepernik, K.; Kim, T.K.; Zimmermann, M.V.; Borisenko, S.V.; Knupfer, M.; Buchner, B.; Geck, J.

    2012-01-01

    We present angle-resolved photoemission studies of (La{1-z}Pr{z}){2-2x}Sr{1+2x}Mn{2}O{7} with x=0.4 and z=0.1, 0.2, and 0.4 along with density functional theory calculations and x-ray scattering data. Our results show that the bilayer splitting in the ferromagnetic metallic phase of these materials

  8. Optical rectification at visible frequency in biased bilayer graphene

    Science.gov (United States)

    Hipolito, F.; Pereira, Vitor M.

    2015-03-01

    The second order response of the electrical current to an electromagnetic field is analyzed within the framework of non-equilibrium many-body perturbation theory for the case of a two-dimensional electronic system such as graphene and its bilayer. The absence of inversion symmetry in a biased graphene bilayer allows a finite DC response in second order to an AC electromagnetic wave. The induced DC current is evaluated for biased bilayer at finite temperature, and its tunability is analyzed as a function of electron density, which can be experimentally varied by means of a global gate voltage applied to the sample. Both intrinsic and photon drag microscopic processes are considered, as they contribute on similar footing to the photocurrent in general. However, the dependencies of these two contributions on the polarization state of the incident light are different, which allows the manipulation of the relative contribution of intrinsic versus photon drag contributions by tuning the experimental parameters. For example, the photocurrent emerging from circularly polarized light stems entirely from photon drag, as the circular photogalvanic effect is forbidden by the C3 rotation symmetry of the honeycomb lattice.

  9. Amphotericin B induced interdigitation of apolipoprotein stabilized nanodisk bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, T; Weers, P M; Sulchek, T; Hoeprich, P D; Ryan, R O

    2006-12-07

    Amphotericin B nanodisks (AMB-ND) are ternary complexes of AMB, phospholipid (PL) and apolipoprotein organized as discrete nanometer scale disk-shaped bilayers. In gel filtration chromatography experiments, empty ND lacking AMB elute as a single population of particles with a molecular weight in the range of 200 kDa. AMB-ND formulated at a 4:1 PL:AMB weight ratio, separated into two peaks. Peak 1 eluted at the position of control ND lacking AMB while the second peak, containing all of the AMB present in the original sample, eluted in the void volume. When ND prepared with increased AMB (1:1 phospholipid:AMB molar ratio) were subjected to gel filtration chromatography, an increased proportion of phospholipid and apolipoprotein were recovered in the void volume with the AMB. Prior to gel filtration the AMB-ND sample could be passed through a 0.22 {micro}m filter without loss of AMB while the voided material was lost. Native gel electrophoresis studies corroborated the gel permeation chromatography data. Far UV circular dichroism analyses revealed that apoA-I associated with AMB-ND denatures at a lower guanidine HCl concentration than apoA-I associated with ND lacking AMB. Atomic force microscopy revealed that AMB induces compression of the ND bilayer thickness consistent with bilayer interdigitation, a phenomenon that is likely related to the ability of AMB to induce pore formation in susceptible membranes.

  10. Odd-parity superconductivity in bilayer transition metal dichalcogenides

    Science.gov (United States)

    Nakamura, Yasuharu; Yanase, Youichi

    2017-08-01

    Spin-orbit coupling in transition metal dichalcogenides (TMDCs) causes spin-valley locking, giving rise to unconventional optical, transport, and superconducting properties. In this paper, we propose exotic superconductivity in bilayer group-IV TMDCs by symmetry control. The sublattice-dependent "hidden" spin-orbit coupling arising from local inversion symmetry breaking in the crystal structure may stabilize the odd-parity superconductivity by purely s -wave local pairing interaction. The stability of the odd-parity superconducting state depends on the bilayer stacking. The 2 Hb stacking in MoX2 and WX2 (X =S ,Se) favors the odd-parity superconductivity due to interlayer quantum interference. On the other hand, the odd-parity superconductivity is suppressed by the 2 Ha stacking of NbSe2. Calculating the phase diagram of the tight-binding model derived from first-principles band calculations, we conclude that the intercalated bilayer MoS2 and WS2 are candidates for a new class of odd-parity superconductors by spin-orbit coupling.

  11. Photon-assisted transport in bilayer graphene flakes

    Science.gov (United States)

    Zambrano, D.; Rosales, L.; Latgé, A.; Pacheco, M.; Orellana, P. A.

    2017-01-01

    The electronic conductance of graphene-based bilayer flake systems reveals different quantum interference effects, such as Fabry-Pérot resonances and sharp Fano antiresonances on account of competing electronic paths through the device. These properties may be exploited to obtain spin-polarized currents when the same nanostructure is deposited above a ferromagnetic insulator. Here, we study how the spin-dependent conductance is affected when a time-dependent gate potential is applied to the bilayer flake. Following a Tien-Gordon formalism, we explore how to modulate the transport properties of such systems via appropriate choices of the ac-field gate parameters. The presence of an oscillating field opens the possibility of tuning the original antiresonances for a large set of field parameters. We show that interference patterns can be partially or fully removed by the time-dependent gate voltage. The results are reflected in the corresponding weighted spin polarization, which can reach maximum values for a given spin component. We found that differential conductance maps as functions of bias and gate potentials show interference patterns for different ac-field parameter configurations. The proposed bilayer graphene flake systems may be used as a frequency detector in the THz range.

  12. Influence of silybin on biophysical properties of phospholipid bilayers

    Institute of Scientific and Technical Information of China (English)

    Olga WESO(L)OWSKA; Krystyna MICHALAK; Barbara (L)ANIA-PIETRZAK; Micha(l) KU(Z)D(Z)A(L); Kamila STA(N)CZAK; Daniela MOSI(A)DZ; Piotr DOBRYSZYCKI; Andrzej O(Z)YHAR; Ma(l)gorzata KOMOROWSKA; Andrzej B HENDRICH

    2007-01-01

    Aim: Silybin (silibinin)is major biologically active flavonolignan extracted from milk thistle (Sylibum marianum). Its biological activities include hepato-protection, anticancer properties, and antioxidant- and membrane-stabilizing functions. Al-though membranes are postulated to be one of the cellular targets for silybin, little is known about its interaction with phospholipid bilayers. Methods: In the present work, the interactions of silybin with phosphatidylcholine bilayers were studied in detail using fluorescence spectroscopy, microcalorimetry and electron spin resonance techniques. Results: The results showed that silybin interacted with the surface of lipid bilayers. It affected the generalized polarization of the fluores-cent probe Prodan, while not influencing the more deeplylocated Laurdan. Silybin lowered the main phospholipid phase transition temperature as judged by microcalorimetry, and caused the immobilization of spin probe Tempo-palmitate located on the surface of membranes. The mobility of spin probes 5-and 16-doxylstearic acid was not affected by silybin. Silybin-induced quenching of 1,6-diphe-nyl-1,3,5-hexatriene fluorescence indicated that some flavonoid molecules parti-tioned into the hydrophobic region of membranes, which did not change signifi-cantly the biophysical properties of the deeper membrane regions. Conclusion: Such a behavior of silybin in membranes is in accordance with its postulated biological functions and neglectable side effects of therapies using silybin.

  13. Thermoelectric Power in Bilayer Graphene Device with Ionic Liquid Gating.

    Science.gov (United States)

    Chien, Yung-Yu; Yuan, Hongtao; Wang, Chang-Ran; Lee, Wei-Li

    2016-01-01

    The quest for materials showing large thermoelectric power has long been one of the important subjects in material science and technology. Such materials have great potential for thermoelectric cooling and also high figure of merit ZT thermoelectric applications. We have fabricated bilayer graphene devices with ionic-liquid gating in order to tune its band gap via application of a perpendicular electric field on a bilayer graphene. By keeping the Fermi level at charge neutral point during the cool-down, we found that the charge puddles effect can be greatly reduced and thus largely improve the transport properties at low T in graphene-based devices using ionic liquid gating. At (Vig, Vbg) = (-1 V, +23 V), a band gap of about 36.6 ± 3 meV forms, and a nearly 40% enhancement of thermoelectric power at T = 120 K is clearly observed. Our works demonstrate the feasibility of band gap tuning in a bilayer graphene using ionic liquid gating. We also remark on the significant influence of the charge puddles effect in ionic-liquid-based devices.

  14. Supercurrent reversal in Josephson junctions based on bilayer graphene flakes

    Science.gov (United States)

    Rameshti, Babak Zare; Zareyan, Malek; Moghaddam, Ali G.

    2015-08-01

    We investigate the Josephson effect in a bilayer graphene flake contacted by two monolayer sheets deposited by superconducting electrodes. It is found that when the electrodes are attached to the different layers of the bilayer, the Josephson current is in a π state, if the bilayer region is undoped and there is no vertical bias. Applying doping or bias to the junction reveals π -0 transitions which can be controlled by varying the temperature and the junction length. The supercurrent reversal here is very different from the ferromagnetic Josephson junctions where the spin degree of freedom plays the key role. We argue that the scattering processes accompanied by layer and sublattice index change give rise to the scattering phases, the effect of which varies with doping and bias. Such scattering phases are responsible for the π -0 transitions. On the other hand, if both of the electrodes are coupled to the same layer of the flake or the flake has AA stacking instead of common AB, the junction will be always in 0 state since the layer or sublattice index is not changed.

  15. Transport spectroscopy in bilayer graphene using double layer heterostructures

    Science.gov (United States)

    Lee, Kayoung; Jung, Jeil; Fallahazad, Babak; Tutuc, Emanuel

    2017-09-01

    We provide a comprehensive study of the chemical potential of bilayer graphene in a wide range of carrier density, at zero and high magnetic (B)-fields, and at different transverse electric (E)-fields, using high quality double bilayer graphene heterostructures. Using a direct thermodynamic transport spectroscopic technique, we probe the chemical potential as a function of carrier density in six samples. The data clearly reveal the non-parabolicity and electron-hole asymmetry of energy-momentum dispersion in bilayer graphene. The tight-binding hopping amplitudes, t 0, t 1, and t 4, renormalized by electron-electron interaction are extracted from the chemical potential versus density dependence. A diverse set of electron-electron interaction driven phenomena were also clearly discerned at zero and high B-fields. We measure the gaps at integer fillings with orbital index N  =  0, 1, and discuss about the dependence of the N  =  0, 1 quantum Hall phases on the carrier density (or filling factor), E-field, and B-field.

  16. Dynamics of Lipid Bilayer Vesicles in Viscous Flows

    Science.gov (United States)

    Schwalbe, Jonathan; Vlahovska, Petia; Miksis, Michael J.

    2008-11-01

    An analytical theory is developed to describe the dynamics of a closed lipid bilayer membrane (vesicle) in a general linear viscous flow. The dynamics of the membrane is governed by the Stokes equations in the fluid plus the normal and tangential stress condition along the bilayer interface. The effects of the membrane fluidity, incompressibility and resistance to bending are taken into account. The model is a generalization of the work on planar membranes by Seifert and Langer (Europhys. Lett. vol. 23, 71, 1993), which accounted for the variations in lipid density along both leaflets of the bilayer. Considering a nearly spherical vesicle, a perturbation solution is derived. The leading order analysis results in a nonlinear coupled system of equations for the dynamics of the shape and the mean lipid density difference between the inner and outer monolayer. Multiple solution states are found as a function of viscosity ratio and the monolayer slip coefficient. The dynamics and stability of these solutions is discussed. Comparisons are made to previous works based on the minimal curvature model which did not consider variable lipid density.

  17. Performance projection of bilayer graphene nanoribbon FET through quantum mechanical simulation

    Science.gov (United States)

    Rawat, Brajesh; Paily, Roy

    2016-12-01

    A quantum transport simulator based on a self-consistent solution of the Schrödinger equation within non-equilibrium Green’s function formalism and 2D Poisson equation for a bilayer graphene nanoribbon (bilayer GNR) field-effect transistor (FET) has been developed to examine the ballistic performance of a device. It is found that the lateral confinement employed in bilayer graphene to form the bilayer GNR largely increases the ON/OFF current ({I}{{ON}}/{I}{{OFF}}) ratios of FET without significantly degrading its ON current ({I}{{ON}}). On the other hand, the interlayer coupling considerably decreases the confinement-induced energy gap of the bilayer GNR and largely increases the {I}{{ON}} of the narrow bilayer GNR FET at the cost of lower {I}{{ON}}/{I}{{OFF}} ratios in comparison with the GNR FET.

  18. The Effect of Bilayer Graphene Nanoribbon Geometry on Schottky-Barrier Diode Performance

    OpenAIRE

    Meisam Rahmani; Razali Ismail; Mohammad Taghi Ahmadi; Mohammad Javad Kiani; Mehdi Saeidmanesh; F. A. Hediyeh Karimi; Elnaz Akbari; Komeil Rahmani

    2013-01-01

    Bilayer graphene nanoribbon is a promising material with outstanding physical and electrical properties that offers a wide range of opportunities for advanced applications in future nanoelectronics. In this study, the application of bilayer graphene nanoribbon in schottky-barrier diode is explored due to its different stacking arrangements. In other words, bilayer graphene nanoribbon schottky-barrier diode is proposed as a result of contact between a semiconductor (AB stacking) and metal (AA ...

  19. Study of annealing effects in Al–Sb bilayer thin films

    Indian Academy of Sciences (India)

    R K Mangal; B Tripathi; M Singh; Y K Vijay

    2007-02-01

    In this paper, we present preparation and characterization of Al–Sb bilayer thin films. Thin films of thicknesses, 3000/1000 Å and 3000/1500 Å, were obtained by the thermal evaporation (resistive heating) method. Vacuum annealing and rapid thermal annealing methods were used to mix bilayer thin film structure. Results obtained from optical band gap data and Rutherford back scattering spectrometry showed mixing of Al–Sb bilayer system.

  20. Time-resolved photoresponse of nanometer-thick Nb/NiCu bilayers

    Science.gov (United States)

    Parlato, L.; Pepe, G. P.; Latempa, R.; De Lisio, C.; Altucci, C.; D'Acunto, P.; Peluso, G.; Barone, A.; Taneda, T.; Sobolewski, R.

    2005-07-01

    We present femtosecond optical time-resolved pump-probe investigations of superconducting hybrids structures consisting of Nb/NiCu bilayers with various thickness. Measurements performed on pure Nb and NiCu films are also given. The photoresponse experiments provide the quasiparticle relaxation times in bilayers of different thickness ratios. The study of the photoresponse as a function of the temperature reveals the spatial evolution of the superconductor order parameter across the bilayers.

  1. Lipid bilayer regulation of membrane protein function: gramicidin channels as molecular force probes

    DEFF Research Database (Denmark)

    Lundbæk, Jens August; Collingwood, S.A.; Ingolfsson, H.I.

    2010-01-01

    physical properties. This advance is because of the introduction of new tools for studying lipid bilayer regulation of protein function. The present review provides an introduction to the regulation of membrane protein function by the bilayer physical properties. We further describe the use of gramicidin...... channels as molecular force probes for studying this mechanism, with a unique ability to discriminate between consequences of changes in monolayer curvature and bilayer elastic moduli....

  2. The effect of calcium on the properties of charged phospholipid bilayers

    DEFF Research Database (Denmark)

    Pedersen, U.R.; Leidy, Chad; Westh, P.

    2006-01-01

    We have performed molecular dynamics simulations to investigate the structure and dynamics of charged bilayers as well as the distribution of counterions at the bilayer interface. For this, we have considered the negatively charged di-myristoyl-phosphatidyl-glycerol (DMPG) and di-myristoyl-phosph......We have performed molecular dynamics simulations to investigate the structure and dynamics of charged bilayers as well as the distribution of counterions at the bilayer interface. For this, we have considered the negatively charged di-myristoyl-phosphatidyl-glycerol (DMPG) and di...

  3. Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

    Science.gov (United States)

    Paula, S.; Volkov, A. G.; Deamer, D. W.

    1998-01-01

    Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

  4. Formation of "solvent-free" black lipid bilayer membranes from glyceryl monooleate dispersed in squalene.

    Science.gov (United States)

    White, S H

    1978-09-01

    A simple technique for forming "black" lipid bilayer membranes containing negligible amounts of alkyl solvent is described. The membranes are formed by the method of Mueller et al (Circulation. 1962. 26:1167.) from glyceryl monooleate (GMO) dispersed in squalene. The squalene forms an annulus to satisfy the boundary conditions of the planar bilayer but does not appear to dissolve noticeably in the bilayer itself. The specific geometric capacitance (Cg) of the membranes at 20 degrees C formed by this technique is 0.7771 +/- 0.0048 muF/cm2. Theoretical estimates of Cg for solvent-free bilayers range from 0.75 to 0.81 muF/cm2. Alkane-free GMO bilayers formed from n-octadecane by the solvent freeze-out method of White (Biochim. Biophys. Acta. 1974. 356:8) have values of Cg = 0.7903 +/- 0.0013 muF/cm2 at 20.5 degrees C. The agreement between the various values of Cg strongly suggests that the bilayers are free of squalene. DC potentials applied to the bilayers have no detectable effect on the value of Cg, as expected for solvent-free films. The ability to form bilayers essentially free of the solvent used in the forming solution makes it possible to determine the area per molecule of the surface active lipid in the bilayer. The area per molecule of GMO at 20 degrees C is estimated to be 37.9 +/- 0.2 A2.

  5. Static and dynamic properties of critical fluctuations in lipid bilayers

    Science.gov (United States)

    Honerkamp-Smith, Aurelia Rose

    A current popular view in cell biology is that sub-micron, dynamic heterogeneity in lipid and protein composition arises within the plasma membranes of resting cells. Local changes in membrane composition may affect protein activity, which is sensitive to the lipid environment. We have observed dynamic heterogeneity in lipid membranes in the form of composition fluctuations near a miscibility critical point. In this thesis we quantitatively describe the dynamic and static properties of these fluctuations. We evaluate the temperature dependence of line tension between liquid domains and of fluctuation correlation lengths in lipid membranes in order to extract a critical exponent, nu. We obtain nu = 1.2 +/- 0.2, consistent with the Ising model prediction nu = 1. From probability distributions of pixel intensities in fluorescence images of membranes, we also extract an independent critical exponent of beta = 0.124 +/- 0.03, which is consistent with the Ising prediction of beta = 1/8. We have systematically measured the effective dynamic critical exponent z eff in a lipid membrane while cooling the system toward a critical point. We observe that zeff slightly increases from a value of roughly 2.6 as xi → 0, to zeff = 3.0 +/- 0.15 at xi = 13 sm. Our measurements are consistent with the prediction that zeff → 3.00 as T → Tc for a 2-D system with conserved order parameter in contact with a bulk 3-D liquid. To our knowledge, no other systematic measurement of zeff with increasing xi exists for a 2-D system with conserved order parameter. We also report the solubility limit of several biologically relevant sterols in electroformed giant unilamellar vesicle membranes containing phosphatidylcholine (PC) lipids in ratios of 1:1:X DPPC:DOPC:sterol. We find solubility limits of cholesterol, lanosterol, ergosterol, stigmasterol, and beta-sitosterol using nuclear magnetic resonance.

  6. Gate induced monolayer behavior in twisted bilayer black phosphorus

    Science.gov (United States)

    Sevik, Cem; Wallbank, John R.; Gülseren, Oğuz; Peeters, François M.; Çakır, Deniz

    2017-09-01

    Optical and electronic properties of black phosphorus strongly depend on the number of layers and type of stacking. Using first-principles calculations within the framework of density functional theory, we investigate the electronic properties of bilayer black phosphorus with an interlayer twist angle of 90°. These calculations are complemented with a simple k\\centerdot p model which is able to capture most of the low energy features and is valid for arbitrary twist angles. The electronic spectrum of 90° twisted bilayer black phosphorus is found to be x-y isotropic in contrast to the monolayer. However x-y anisotropy, and a partial return to monolayer-like behavior, particularly in the valence band, can be induced by an external out-of-plane electric field. Moreover, the preferred hole effective mass can be rotated by 90° simply by changing the direction of the applied electric field. In particular, a + 0.4 (-0.4) V {{{\\mathringA}}-1} out-of-plane electric field results in a  ˜60% increase in the hole effective mass along the \\mathbf{y} (\\mathbf{x} ) axis and enhances the m\\mathbf{y}\\ast/m\\mathbf{x}\\ast (m\\mathbf{x}\\ast/m\\mathbf{y}\\ast ) ratio as much as by a factor of 40. Our DFT and k\\centerdot p simulations clearly indicate that the twist angle in combination with an appropriate gate voltage is a novel way to tune the electronic and optical properties of bilayer phosphorus and it gives us a new degree of freedom to engineer the properties of black phosphorus based devices.

  7. Interaction of curcumin with lipid monolayers and liposomal bilayers.

    Science.gov (United States)

    Karewicz, Anna; Bielska, Dorota; Gzyl-Malcher, Barbara; Kepczynski, Mariusz; Lach, Radosław; Nowakowska, Maria

    2011-11-01

    Curcumin shows huge potential as an anticancer and anti-inflammatory agent. However, to achieve a satisfactory bioavailability and stability of this compound, its liposomal form is preferable. Our detailed studies on the curcumin interaction with lipid membranes are aimed to obtain better understanding of the mechanism and eventually to improve the efficiency of curcumin delivery to cells. Egg yolk phosphatidylcholine (EYPC) one-component monolayers and bilayers, as well as mixed systems containing additionally dihexadecyl phosphate (DHP) and cholesterol, were studied. Curcumin binding constant to EYPC liposomes was determined based on two different methods: UV/Vis absorption and fluorescence measurements to be 4.26×10(4)M(-1) and 3.79×10(4)M(-1), respectively. The fluorescence quenching experiment revealed that curcumin locates in the hydrophobic region of EYPC liposomal bilayer. It was shown that curcumin impacts the size and stability of the liposomal carriers significantly. Loaded into the EYPC/DPH/cholesterol liposomal bilayer curcumin stabilizes the system proportionally to its content, while the EYPC/DPH system is destabilized upon drug loading. The three-component lipid composition of the liposome seems to be the most promising system for curcumin delivery. An interaction of free and liposomal curcumin with EYPC and mixed monolayers was also studied using Langmuir balance measurements. Monolayer systems were treated as a simple model of cell membrane. Condensing effect of curcumin on EYPC and EYPC/DHP monolayers and loosening influence on EYPC/DHP/chol ones were observed. It was also demonstrated that curcumin-loaded EYPC liposomes are more stable upon interaction with the model lipid membrane than the unloaded ones.

  8. Giant Frictional Drag in Double Bilayer Graphene Heterostructures

    Science.gov (United States)

    Lee, Kayoung; Xue, Jiamin; Dillen, David C.; Watanabe, Kenji; Taniguchi, Takashi; Tutuc, Emanuel

    2016-07-01

    We study the frictional drag between carriers in two bilayer graphene flakes separated by a 2-5 nm thick hexagonal boron nitride dielectric. At temperatures (T ) lower than ˜10 K , we observe a large anomalous negative drag emerging predominantly near the drag layer charge neutrality. The anomalous drag resistivity increases dramatically with reducing T , and becomes comparable to the layer resistivity at the lowest T =1.5 K . At low T the drag resistivity exhibits a breakdown of layer reciprocity. A comparison of the drag resistivity and the drag layer Peltier coefficient suggests a thermoelectric origin of this anomalous drag.

  9. Band Structure Asymmetry of Bilayer Graphene Revealed by Infrared Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Li, Z.Q.; Henriksen, E.A.; Jiang, Z.; Hao, Zhao; Martin, Michael C.; Kim, P.; Stormer, H.L.; Basov, Dimitri N.

    2008-12-10

    We report on infrared spectroscopy of bilayer graphene integrated in gated structures. We observe a significant asymmetry in the optical conductivity upon electrostatic doping of electrons and holes. We show that this finding arises from a marked asymmetry between the valence and conduction bands, which is mainly due to the inequivalence of the two sublattices within the graphene layer and the next-nearest-neighbor interlayer coupling. From the conductivity data, the energy difference of the two sublattices and the interlayer coupling energy are directly determined.

  10. Multicritical point in a diluted bilayer Heisenberg quantum antiferromagnet.

    Science.gov (United States)

    Sandvik, Anders W

    2002-10-21

    The S=1/2 Heisenberg bilayer antiferromagnet with randomly removed interlayer dimers is studied using quantum Monte Carlo simulations. A zero-temperature multicritical point (p(*),g(*)) at the classical percolation density p=p(*) and interlayer coupling g(*) approximately equal 0.16 is demonstrated. The quantum critical exponents of the percolating cluster are determined using finite-size scaling. It is argued that the associated finite-temperature quantum critical regime extends to zero interlayer coupling and could be relevant for antiferromagnetic cuprates doped with nonmagnetic impurities.

  11. Tailored sequential drug release from bilayered calcium sulfate composites

    Energy Technology Data Exchange (ETDEWEB)

    Orellana, Bryan R.; Puleo, David A., E-mail: puleo@uky.edu

    2014-10-01

    The current standard for treating infected bony defects, such as those caused by periodontal disease, requires multiple time-consuming steps and often multiple procedures to fight the infection and recover lost tissue. Releasing an antibiotic followed by an osteogenic agent from a synthetic bone graft substitute could allow for a streamlined treatment, reducing the need for multiple surgeries and thereby shortening recovery time. Tailorable bilayered calcium sulfate (CS) bone graft substitutes were developed with the ability to sequentially release multiple therapeutic agents. Bilayered composite samples having a shell and core geometry were fabricated with varying amounts (1 or 10 wt.%) of metronidazole-loaded poly(lactic-co-glycolic acid) (PLGA) particles embedded in the shell and simvastatin directly loaded into either the shell, core, or both. Microcomputed tomography showed the overall layered geometry as well as the uniform distribution of PLGA within the shells. Dissolution studies demonstrated that the amount of PLGA particles (i.e., 1 vs. 10 wt.%) had a small but significant effect on the erosion rate (3% vs. 3.4%/d). Mechanical testing determined that introducing a layered geometry had a significant effect on the compressive strength, with an average reduction of 35%, but properties were comparable to those of mandibular trabecular bone. Sustained release of simvastatin directly loaded into CS demonstrated that changing the shell to core volume ratio dictates the duration of drug release from each layer. When loaded together in the shell or in separate layers, sequential release of metronidazole and simvastatin was achieved. By introducing a tunable, layered geometry capable of releasing multiple drugs, CS-based bone graft substitutes could be tailored in order to help streamline the multiple steps needed to regenerate tissue in infected defects. - Highlights: • Bilayered CS composites were fabricated as potential bone graft substitutes. • The shell

  12. Phase Diagram of Antiferromagnetically Exchange-Coupled Bilayer

    Institute of Scientific and Technical Information of China (English)

    GUO Guang-Hua; ZHANG Guang-Fu; SUN Li-Yuan; Peter A. J. de Groot

    2008-01-01

    Magnetic hysteresis properties of antiferromagnetically exchange-coupled bilayer structures, in which the two magnetic layers have different magnetic parameters and thicknesses, are studied within the framework of the Stoner-Wohifarth model. Analytical expressions for the switching fields corresponding to the linear magnetic states are obtained. By adjusting the magnetic parameters or thicknesses of layers, nine different types of easyaxis hysteresis loops may exist. The phase diagram of easy-axis hysteresis loops is mapped in the k,1 and k,2 plane, where k,1 and k,2 are the ratios of magnetic anisotropy to the interlayer exchange coupling of the two magnetic layers, respectively.

  13. Negative terahertz conductivity in remotely doped graphene bilayer heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Ryzhii, V. [Research Institute of Electrical Communication, Tohoku University, Sendai 980-8577 (Japan); Institute of Ultra High Frequency Semiconductor Electronics of RAS, and Center for Photonics and Infrared Engineering, Bauman Moscow State Technical University, Moscow 111005 (Russian Federation); Ryzhii, M. [Department of Computer Science and Engineering, University of Aizu, Aizu-Wakamatsu 965-8580 (Japan); Mitin, V. [Department of Electrical Engineering, University at Buffalo, SUNY, Buffalo, New York 1460-1920 (United States); Shur, M. S. [Departments of Electrical, Electronics, and Systems Engineering and Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, New York 12180 (United States); Otsuji, T. [Research Institute of Electrical Communication, Tohoku University, Sendai 980-8577 (Japan)

    2015-11-14

    Injection or optical generation of electrons and holes in graphene bilayers (GBLs) can result in the interband population inversion enabling the terahertz (THz) radiation lasing. The intraband radiative processes compete with the interband transitions. We demonstrate that remote doping enhances the indirect interband generation of photons in the proposed GBL heterostructures. Therefore, such remote doping helps to surpass the intraband (Drude) absorption, and results in large absolute values of the negative dynamic THz conductivity in a wide range of frequencies at elevated (including room) temperatures. The remotely doped GBL heterostructure THz lasers are expected to achieve higher THz gain compared with previously proposed GBL-based THz lasers.

  14. Ultraviolet-induced erasable photochromism in bilayer metal oxide films

    Science.gov (United States)

    Terakado, Nobuaki; Tanaka, Keiji; Nakazawa, Akira

    2011-09-01

    We demonstrate that the optical transmittance of bilayer samples consisting of pyrolytically coated amorphous Mg-Sn-O and metal oxide films such as In 2O 3 and SnO 2 decreases upon ultraviolet illumination, but can be recovered by annealing in air at ˜300 ∘C. Spectral, structural, and compositional studies suggest that this photochromic phenomenon is induced by photoelectronic excitation in the Mg-Sn-O film, electron injection into the metal oxide, which becomes negatively charged, and subsequent formation of metallic particles, which absorb and/or scatter visible light.

  15. Electronic Bloch oscillation in bilayer graphene gradient superlattices

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Hemeng; Li, Changan; Song, Yun [Department of Physics, Beijing Normal University, Beijing 100875 (China); Ma, Tianxing, E-mail: txma@bnu.edu.cn [Department of Physics, Beijing Normal University, Beijing 100875 (China); Beijing Computational Science Research Center, Beijing 100084 (China); Wang, Li-Gang, E-mail: sxwlg@yahoo.com [Department of Physics, Zhejiang University, Hangzhou 310027 (China); Lin, Hai-Qing [Beijing Computational Science Research Center, Beijing 100084 (China)

    2014-08-18

    We investigate the electronic Bloch oscillation in bilayer graphene gradient superlattices using transfer matrix method. By introducing two kinds of gradient potentials of square barriers along electrons propagation direction, we find that Bloch oscillations up to terahertz can occur. Wannier-Stark ladders, as the counterpart of Bloch oscillation, are obtained as a series of equidistant transmission peaks, and the localization of the electronic wave function is also signature of Bloch oscillation. Furthermore, the period of Bloch oscillation decreases linearly with increasing gradient of barrier potentials.

  16. Twisting dirac fermions: circular dichroism in bilayer graphene

    Science.gov (United States)

    Suárez Morell, E.; Chico, Leonor; Brey, Luis

    2017-09-01

    Twisted bilayer graphene is a chiral system which has been recently shown to present circular dichroism. In this work we show that the origin of this optical activity is the rotation of the Dirac fermions’ helicities in the top and bottom layer. Starting from the Kubo formula, we obtain a compact expression for the Hall conductivity that takes into account the dephasing of the electromagnetic field between the top and bottom layers and gathers all the symmetries of the system. Our results are based in both a continuum and a tight-binding model, and they can be generalized to any two-dimensional Dirac material with a chiral stacking between layers.

  17. Inverse Proximity Effect in Superconductor-ferromagnet Bilayer Structures

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Jing

    2010-04-05

    Measurements of the polar Kerr effect using a zero-area-loop Sagnac magnetometer on Pb/Ni and Al/(Co-Pd) proximity-effect bilayers show unambiguous evidence for the 'inverse proximity effect,' in which the ferromagnet (F) induces a finite magnetization in the superconducting (S) layer. To avoid probing the magnetic effects in the ferromagnet, the superconducting layer was prepared much thicker than the light's optical penetration depth. The sign and size of the effect, as well as its temperature dependence agree with recent predictions by Bergeret et al.[1].

  18. Monte Carlo simulation of charge mediated magnetoelectricity in multiferroic bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz-Álvarez, H.H. [Universidad de Caldas, Manizales (Colombia); Universidad Nacional de Colombia Sede Manizales, Manizales, Caldas (Colombia); Bedoya-Hincapié, C.M. [Universidad Nacional de Colombia Sede Manizales, Manizales, Caldas (Colombia); Universidad Santo Tomás, Bogotá (Colombia); Restrepo-Parra, E., E-mail: erestrepopa@unal.edu.co [Universidad Nacional de Colombia Sede Manizales, Manizales, Caldas (Colombia)

    2014-12-01

    Simulations of a bilayer ferroelectric/ferromagnetic multiferroic system were carried out, based on the Monte Carlo method and Metropolis dynamics. A generic model was implemented with a Janssen-like Hamiltonian, taking into account magnetoelectric interactions due to charge accumulation at the interface. Two different magnetic exchange constants were considered for accumulation and depletion states. Several screening lengths were also included. Simulations exhibit considerable magnetoelectric effects not only at low temperature, but also at temperature near to the transition point of the ferromagnetic layer. The results match experimental observations for this kind of structure and mechanism.

  19. Small-angle neutron scattering from multilamellar lipid bilayers: Theory, model, and experiment

    DEFF Research Database (Denmark)

    Lemmich, Jesper; Mortensen, Kell; Ipsen, John Hjorth

    1996-01-01

    Small-angle neutron scattering data obtained from fully hydrated, multilamellar phospholipid bilayers with deuterated acyl chains of different length are presented and analyzed within a paracrystalline theory and a geometric model that permit the bilayer structure to be determined under condition...

  20. Lindane Suppresses the Lipid-bilayer Permeability in Main Transition Region

    DEFF Research Database (Denmark)

    Sabra, Mads Christian; Jørgensen, Kent; Mouritsen, Ole G.

    1996-01-01

    %) of lindane. Fluorescence spectroscopy was used to measure the passive permeability of unilamellar DMPC bilayers to Co2+ ions. The data show that lindane seals the bilayer for Co2+ penetration and that this effect increases with increasing lindane concentration. The results are discussed in relation...... to the effects on the permeability of other small molecules, e.g., anesthetics....

  1. Solid-supported monolayers and bilayers of amphiphilic ß-Cyclodextrin

    NARCIS (Netherlands)

    Cristiano, Antonella; Lim, C.W.; Rozkiewicz, D.I.; Reinhoudt, David; Ravoo, B.J.

    2007-01-01

    This paper describes the adsorption and spreading of B-cyclodextrin (CD) vesicles on hydrophobic and hydrophilic substrates, which involves a transition from bilayer vesicles to planar molecular monolayers or bilayers. On substrates that are patterned with self-assembled monolayers by microcontact

  2. Sign reversal of drag in bilayer systems with in-plane periodic potential modulation

    DEFF Research Database (Denmark)

    Alkauskas, A.; Flensberg, Karsten; Hu, Ben Yu-Kuang;

    2002-01-01

    We develop a theory for describing frictional drag in bilayer systems with in-plane periodic potential modulations, and use it to investigate the drag between bilayer systems in which one of the layers is modulated in one direction. At low temperatures, as the density of carriers in the modulated...

  3. Alginate based bilayer hydrocolloid films as potential slow-release modern wound dressing.

    Science.gov (United States)

    Thu, Hnin-Ei; Zulfakar, Mohd Hanif; Ng, Shiow-Fern

    2012-09-15

    The aims of this research were to develop a novel bilayer hydrocolloid film based on alginate and to investigate its potential as slow-release wound healing vehicle. The bilayer is composed of an upper layer impregnated with model drug (ibuprofen) and a drug-free lower layer, which acted as a rate-controlling membrane. The thickness uniformity, solvent loss, moisture vapour transmission rate (MVTR), hydration rate, morphology, rheology, mechanical properties, in vitro drug release and in vivo wound healing profiles were investigated. A smooth bilayer film with two homogenous distinct layers was produced. The characterisation results showed that bilayer has superior mechanical and rheological properties than the single layer films. The bilayers also showed low MVTR, slower hydration rate and lower drug flux in vitro compared to single layer inferring that bilayer may be useful for treating low suppurating wounds and suitable for slow release application on wound surfaces. The bilayers also provided a significant higher healing rate in vivo, with well-formed epidermis with faster granulation tissue formation when compared to the controls. In conclusions, a novel alginate-based bilayer hydrocolloid film was developed and results suggested that they can be exploited as slow-release wound dressings.

  4. Regulation of membrane protein function by lipid bilayer elasticity—a single molecule technology to measure the bilayer properties experienced by an embedded protein

    DEFF Research Database (Denmark)

    Lundbæk, Jens August

    2008-01-01

    , in the general regulation of membrane protein function, is unclear. This is to a large extent due to lack of a generally accepted framework in which to understand the many observations. The present review summarizes studies which have demonstrated that the hydrophobic interactions between a membrane protein...... and the host lipid bilayer provide an energetic coupling, whereby protein function can be regulated by the bilayer elasticity. The feasibility of this ‘hydrophobic coupling mechanism’ has been demonstrated using the gramicidin channel, a model membrane protein, in planar lipid bilayers. Using voltage...... properties experienced by an embedded protein has been developed. A theoretical and technological framework, to study the regulation of membrane protein function by lipid bilayer elasticity, has been established....

  5. Specific heat of twisted bilayer graphene: Engineering phonons by atomic plane rotations

    Energy Technology Data Exchange (ETDEWEB)

    Nika, Denis L. [E. Pokatilov Laboratory of Physics and Engineering of Nanomaterials, Department of Physics and Engineering, Moldova State University, Chisinau MD-2009, Republic of Moldova (Moldova, Republic of); Nano-Device Laboratory, Department of Electrical Engineering and Materials Science and Engineering Program, Bourns College of Engineering, University of California—Riverside, Riverside, California, 92521 (United States); Cocemasov, Alexandr I. [E. Pokatilov Laboratory of Physics and Engineering of Nanomaterials, Department of Physics and Engineering, Moldova State University, Chisinau MD-2009, Republic of Moldova (Moldova, Republic of); Balandin, Alexander A., E-mail: balandin@ee.ucr.edu [Nano-Device Laboratory, Department of Electrical Engineering and Materials Science and Engineering Program, Bourns College of Engineering, University of California—Riverside, Riverside, California, 92521 (United States)

    2014-07-21

    We have studied the phonon specific heat in single-layer, bilayer, and twisted bilayer graphene. The calculations were performed using the Born-von Karman model of lattice dynamics for intralayer atomic interactions and spherically symmetric interatomic potential for interlayer interactions. We found that at temperature T < 15 K, specific heat varies with temperature as T{sup n}, where n = 1 for graphene, n = 1.6 for bilayer graphene, and n = 1.3 for the twisted bilayer graphene. The phonon specific heat reveals an intriguing dependence on the twist angle in bilayer graphene, which is particularly pronounced at low temperature. The results suggest a possibility of phonon engineering of thermal properties of layered materials by twisting the atomic planes.

  6. CONTEMPORARY APPROACHES FOR BI-LAYER TECHNOLOGY OF DRUGS THROUGH ORAL ROUTE: AN OVERVIEW

    Directory of Open Access Journals (Sweden)

    Rishikesh*, M. A. Bhuiyan, S. M. Ashraful Islam, I. Dewan, Md. A. Islam and Md. S.- Ul H. Miah

    2013-04-01

    Full Text Available ABSTRACT: Bi-layer tablet technology for bimodal release of drug and co-administration of drugs via oral route has been engaged a significant place in the field of drug delivery technology. At present, several pharmaceutical companies are developing bilayer tablet for co-administration of drugs to improve the therapeutic efficacy as well as to reduce the chances of drug-drug interaction. This review indicates the different aspects of drug release mechanism, different strategies of drug release, various techniques for bilayer tablet, and the influence of different process and formulation parameters must be considered during the development of bilayer tablet. Bi-layer tablet is suitable for sequential release of two drugs in combination, separate two incompatible substances, and also for sustained release tablet in which one layer is immediate release as initial dose and second layer is maintenance dose.

  7. Growth and characterization of the ZnO/ZnS bilayer obtained by chemical spray pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, M.C. [Laboratorio de Materiales y Superficie (Unidad Asociada al CSIC), Dptos Fisica Aplicada and Dpto Ingenieria Quimica, Facultad de Ciencias, Universidad de Malaga, E29071 Malaga (Spain); Espinos, J.P. [Instituto de Ciencias de Materiales de Sevilla (CSIC), Avda. Americo Vespucio s/n, E41092 Sevilla (Spain); Leinen, D.; Martin, F. [Laboratorio de Materiales y Superficie (Unidad Asociada al CSIC), Dptos Fisica Aplicada and Dpto Ingenieria Quimica, Facultad de Ciencias, Universidad de Malaga, E29071 Malaga (Spain); Centeno, S.P. [Departamento de Quimica-Fisica, Facultad de Ciencias, Universidad de Malaga, E29071 Malaga (Spain); Romero, R. [Laboratorio de Materiales y Superficie (Unidad Asociada al CSIC), Dptos Fisica Aplicada and Dpto Ingenieria Quimica, Facultad de Ciencias, Universidad de Malaga, E29071 Malaga (Spain); Ramos-Barrado, J.R. [Laboratorio de Materiales y Superficie (Unidad Asociada al CSIC), Dptos Fisica Aplicada and Dpto Ingenieria Quimica, Facultad de Ciencias, Universidad de Malaga, E29071 Malaga (Spain)], E-mail: barrado@uma.es

    2008-12-30

    ZnO/ZnS bilayer antireflection coatings have been prepared by spray pyrolysis using aqueous solutions of zinc acetate and thiourea or zinc chloride and thiourea. The structure, surface morphology, chemical composition and optical transmittance of the bilayer have been examined as a function of the composition of the initial solution. X-ray photoelectron spectroscopy analysis and Ar ion-beam sputter etching was carried out to obtain a depth profile of bilayer. Neither carbon nor other by-products, which could alter the optical transmittance of the bilayer were found in either the interface or bulk. The differences between the bilayers arise from the annealing of the ZnS underlayer, as well as the precursor used to prepare it.

  8. Filament networks attached to membranes: cytoskeletal pressure and local bilayer deformation

    Science.gov (United States)

    Auth, Thorsten; Safran, S. A.; Gov, Nir S.

    2007-11-01

    Several cell types, among them red blood cells, have a cortical, two-dimensional (2D) network of filaments sparsely attached to their lipid bilayer. In many mammalian cells, this 2D polymer network is connected to an underlying 3D, more rigid cytoskeleton. In this paper, we consider the pressure exerted by the thermally fluctuating, cortical network of filaments on the bilayer and predict the bilayer deformations that are induced by this pressure. We treat the filaments as flexible polymers and calculate the pressure that a network of such linear chains exerts on the bilayer; we then minimize the bilayer shape in order to predict the resulting local deformations. We compare our predictions with membrane deformations observed in electron micrographs of red blood cells. The polymer pressure along with the resulting membrane deformation can lead to compartmentalization, regulate in-plane diffusion and may influence protein sorting as well as transmit signals to the polymerization of the underlying 3D cytoskeleton.

  9. Intrinsic magnetism and spontaneous band gap opening in bilayer silicene and germanene.

    Science.gov (United States)

    Wang, Xinquan; Wu, Zhigang

    2017-01-18

    It has been long sought to create magnetism out of simple non-magnetic materials, such as silicon and germanium. Here we show that intrinsic magnetism exists in bilayer silicene and germanene with no need to cut, etch, or dope. Unlike bilayer graphene, strong covalent interlayer bonding formed in bilayer silicene and germanene breaks the original π-bonding network of each layer, leaving the unbonded electrons unpaired and localized to carry magnetic moments. These magnetic moments then couple ferromagnetically within each layer while antiferromagnetically across two layers, giving rise to an infinite magnetic sheet with structural integrity and magnetic homogeneity. Furthermore, this unique magnetic ordering results in fundamental band gaps of 0.55 eV and 0.32 eV for bilayer silicene and germanene, respectively. The integration of intrinsic magnetism and spontaneous band gap opening makes bilayer silicene and germanene attractive for future nanoelectronics as well as spin-based computation and data storage.

  10. A simple method to tune graphene growth between monolayer and bilayer

    Directory of Open Access Journals (Sweden)

    Xiaozhi Xu

    2016-02-01

    Full Text Available Selective growth of either monolayer or bilayer graphene is of great importance. We developed a method to readily tune large area graphene growth from complete monolayer to complete bilayer. In an ambient pressure chemical vapor deposition process, we used the sample temperature at which to start the H2 flow as the control parameter and realized the change from monolayer to bilayer growth of graphene on Cu foil. When the H2 starting temperature was above 700°C, continuous monolayer graphene films were obtained. When the H2 starting temperature was below 350°C, continuous bilayer films were obtained. Detailed characterization of the samples treated under various conditions revealed that heating without the H2 flow caused Cu oxidation. The more the Cu substrate oxidized, the less graphene bilayer could form.

  11. X-Ray Kinematography of Temperature-Jump Relaxation Probes the Elastic Properties of Fluid Bilayers

    CERN Document Server

    Pabst, G; Amenitsch, H; Bernstorff, S; Laggner, P; Pabst, Georg; Rappolt, Michael; Amenitsch, Heinz; Bernstorff, Sigrid; Laggner, Peter

    2000-01-01

    The response kinetics of liquid crystalline phosphatidylcholine bilayerstacks to rapid, IR-laser induced temperature jumps has been studied bymillisecond time-resolved x-ray diffraction. The system reacts on the fasttemperature change by a discrete bilayer compression normal to its surface anda lateral bilayer expansion. Since water cannot diffuse from the excess phaseinto the interbilayer water region within the 2 ms duration of the laser pulse,the water layer has to follow the bilayer expansion, by an anomalous thinning.Structural analysis of a 20 ms diffraction pattern from the intermediate phaseindicates that the bilayer thickness remains within the limits of isothermalequilibrium values. Both, the intermediate structure and its relaxation intothe original equilibrium L_(alpha)-phase, depend on the visco-elasticproperties of the bilayer/water system. We present an analysis of therelaxation process by an overdamped one-dimensional oscillation model revealingthe concepts of Hooke's law for phospholipid bila...

  12. Removal of the mechanoprotective influence of the cytoskeleton reveals PIEZO1 is gated by bilayer tension

    Science.gov (United States)

    Cox, Charles D.; Bae, Chilman; Ziegler, Lynn; Hartley, Silas; Nikolova-Krstevski, Vesna; Rohde, Paul R.; Ng, Chai-Ann; Sachs, Frederick; Gottlieb, Philip A.; Martinac, Boris

    2016-01-01

    Mechanosensitive ion channels are force-transducing enzymes that couple mechanical stimuli to ion flux. Understanding the gating mechanism of mechanosensitive channels is challenging because the stimulus seen by the channel reflects forces shared between the membrane, cytoskeleton and extracellular matrix. Here we examine whether the mechanosensitive channel PIEZO1 is activated by force-transmission through the bilayer. To achieve this, we generate HEK293 cell membrane blebs largely free of cytoskeleton. Using the bacterial channel MscL, we calibrate the bilayer tension demonstrating that activation of MscL in blebs is identical to that in reconstituted bilayers. Utilizing a novel PIEZO1-GFP fusion, we then show PIEZO1 is activated by bilayer tension in bleb membranes, gating at lower pressures indicative of removal of the cortical cytoskeleton and the mechanoprotection it provides. Thus, PIEZO1 channels must sense force directly transmitted through the bilayer.

  13. Anomalous swelling of multilamellar lipid bilayers in the transition region by renormalization of curvature elasticity

    DEFF Research Database (Denmark)

    Callisen, Thomas Hønger; Mortensen, Kell; Ipsen, John Hjorth

    1994-01-01

    Small-angle neutron scattering is used to determine the temperature dependence of the lamellar repeat distance in an aqueous multilamellar solution of phospholipid bilayers. A thermal anomaly in the swelling behavior is observed at the bilayer phase transition. The anomalous behavior can be suppr......Small-angle neutron scattering is used to determine the temperature dependence of the lamellar repeat distance in an aqueous multilamellar solution of phospholipid bilayers. A thermal anomaly in the swelling behavior is observed at the bilayer phase transition. The anomalous behavior can...... be suppressed by varying the lipid acyl-chain length or by alloying with a molecular stiffening agent. The experimental results are explained in terms of renormalization of the bilayer curvature elasticity and by using a theory of repulsive interlamellar undulation forces....

  14. Filament networks attached to membranes: cytoskeletal pressure and local bilayer deformation

    Energy Technology Data Exchange (ETDEWEB)

    Auth, Thorsten [Department of Materials and Interfaces, Weizmann Institute of Science, PO Box 26, Rehovot 76100 (Israel); Safran, S A [Department of Materials and Interfaces, Weizmann Institute of Science, PO Box 26, Rehovot 76100 (Israel); Gov, Nir S [Department of Chemical Physics, Weizmann Institute of Science, PO Box 26, Rehovot 76100 (Israel)

    2007-11-15

    Several cell types, among them red blood cells, have a cortical, two-dimensional (2D) network of filaments sparsely attached to their lipid bilayer. In many mammalian cells, this 2D polymer network is connected to an underlying 3D, more rigid cytoskeleton. In this paper, we consider the pressure exerted by the thermally fluctuating, cortical network of filaments on the bilayer and predict the bilayer deformations that are induced by this pressure. We treat the filaments as flexible polymers and calculate the pressure that a network of such linear chains exerts on the bilayer; we then minimize the bilayer shape in order to predict the resulting local deformations. We compare our predictions with membrane deformations observed in electron micrographs of red blood cells. The polymer pressure along with the resulting membrane deformation can lead to compartmentalization, regulate in-plane diffusion and may influence protein sorting as well as transmit signals to the polymerization of the underlying 3D cytoskeleton.

  15. Ground states of bilayered and extended t-J-U models

    Energy Technology Data Exchange (ETDEWEB)

    Voo, Khee-Kyun, E-mail: kkvoo@mail.oit.edu.tw

    2015-09-04

    The ground states of bilayered and extended t-J-U models are investigated with renormalized mean field theory. The trial wave functions are Gutzwiller projected Hartree–Fock states, and the site double occupancies are variational parameters. It is found that a spontaneous interlayer phase separation (PS) may arise in bilayers. In electron–hole doping asymmetric systems, the propensity for PS is stronger in electron doped bands. Via a PS, superconductivity can survive to lower doping densities, and antiferromagnetism in electron doped systems may survive to higher doping densities. The result is related to the superconducting cuprates. - Highlights: • Ground states in doped bilayered t-J-U models are studied. • Variational wave functions are Gutzwiller projected wave functions. • Site double occupancies are variational parameters. • Spontaneous interlayer phase separation may occur in bilayers. • Stronger tendency toward phase separation in electron doped bilayers.

  16. Non-periodic molecular dynamics simulations of coarse grained lipid bilayer in water

    DEFF Research Database (Denmark)

    Kotsalis, E. M.; Hanasaki, I.; Walther, Jens Honore

    2010-01-01

    We present a multiscale algorithm that couples coarse grained molecular dynamics (CGMD) with continuum solver. The coupling requires the imposition of non-periodic boundary conditions on the coarse grained Molecular Dynamics which, when not properly enforced, may result in spurious fluctuations...... of the material properties of the system represented by CGMD. In this paper we extend a control algorithm originally developed for atomistic simulations [3], to conduct simulations involving coarse grained water molecules without periodic boundary conditions. We demonstrate the applicability of our method...... in simulating more complex systems by performing a non-periodic Molecular Dynamics simulation of a DPPC lipid in liquid coarse grained water....

  17. Modeling the Elastic Properties of Lipid Bilayer Membranes

    Science.gov (United States)

    Barry, Edward; Gibaud, Thomas; Zakhary, Mark; Dogic, Zvonimir

    2011-03-01

    Model membranes such as lipid bilayers have been indispensable tools for our understanding of the elastic properties of biological membranes. In this talk, I will introduce a colloidal model for membranes and demonstrate that the physical properties of these colloidal membranes are identical to lipid bilayers. The model system is unique in that the constituent molecules are homogenous and non-amphiphilic, yet their self-assembly into membranes and other hierarchical assemblages, such as a lamellar type phases and chiral ribbons, proceeds spontaneously in solution. Owing to the large size of the constituent molecules, individual molecules can be directly visualized and simultaneous observations at the continuum and molecular lengthscales are used to characterize the behavior of model membranes with unprecedented detail. Moreover, once assembled in solution, molecular interactions can be controlled in situ. In particular, the strength of chiral interactions can be varied, leading to fascinating transitions in behavior that resembles the formation of starfish vesicles. These observations point towards the important role of line tension, and have potential implications for phase separated lipid mixtures or lipid rafts.

  18. Surface and interfacial creases in a bilayer tubular soft tissue

    Science.gov (United States)

    Razavi, Mir Jalil; Pidaparti, Ramana; Wang, Xianqiao

    2016-08-01

    Surface and interfacial creases induced by biological growth are common types of instability in soft biological tissues. This study focuses on the criteria for the onset of surface and interfacial creases as well as their morphological evolution in a growing bilayer soft tube within a confined environment. Critical growth ratios for triggering surface and interfacial creases are investigated both analytically and numerically. Analytical interpretations provide preliminary insights into critical stretches and growth ratios for the onset of instability and formation of both surface and interfacial creases. However, the analytical approach cannot predict the evolution pattern of the model after instability; therefore nonlinear finite element simulations are carried out to replicate the poststability morphological patterns of the structure. Analytical and computational simulation results demonstrate that the initial geometry, growth ratio, and shear modulus ratio of the layers are the most influential factors to control surface and interfacial crease formation in this soft tubular bilayer. The competition between the stretch ratios in the free and interfacial surfaces is one of the key driving factors to determine the location of the first crease initiation. These findings may provide some fundamental understanding in the growth modeling of tubular biological tissues such as esophagi and airways as well as offering useful clues into normal and pathological functions of these tissues.

  19. Multiscale modeling of droplet interface bilayer membrane networks.

    Science.gov (United States)

    Freeman, Eric C; Farimani, Amir B; Aluru, Narayana R; Philen, Michael K

    2015-11-01

    Droplet interface bilayer (DIB) networks are considered for the development of stimuli-responsive membrane-based materials inspired by cellular mechanics. These DIB networks are often modeled as combinations of electrical circuit analogues, creating complex networks of capacitors and resistors that mimic the biomolecular structures. These empirical models are capable of replicating data from electrophysiology experiments, but these models do not accurately capture the underlying physical phenomena and consequently do not allow for simulations of material functionalities beyond the voltage-clamp or current-clamp conditions. The work presented here provides a more robust description of DIB network behavior through the development of a hierarchical multiscale model, recognizing that the macroscopic network properties are functions of their underlying molecular structure. The result of this research is a modeling methodology based on controlled exchanges across the interfaces of neighboring droplets. This methodology is validated against experimental data, and an extension case is provided to demonstrate possible future applications of droplet interface bilayer networks.

  20. Unidirectional spin Hall magnetoresistance in ferromagnet/normal metal bilayers

    Science.gov (United States)

    Avci, Can Onur; Garello, Kevin; Ghosh, Abhijit; Gabureac, Mihai; Alvarado, Santos F.; Gambardella, Pietro

    2015-07-01

    Magnetoresistive effects are usually invariant on inversion of the magnetization direction. In non-centrosymmetric conductors, however, nonlinear resistive terms can give rise to a current dependence that is quadratic in the applied voltage and linear in the magnetization. Here we demonstrate that such conditions are realized in simple bilayer metal films where the spin-orbit interaction and spin-dependent scattering couple the current-induced spin accumulation to the electrical conductivity. We show that the longitudinal resistance of Ta|Co and Pt|Co bilayers changes when reversing the polarity of the current or the sign of the magnetization. This unidirectional magnetoresistance scales linearly with current density and has opposite sign in Ta and Pt, which we associate with the modification of the interface scattering potential induced by the spin Hall effect in these materials. Our results suggest a route to control the resistance and detect magnetization switching in spintronic devices using a two-terminal geometry, which applies also to heterostructures including topological insulators.

  1. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires

    Science.gov (United States)

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P.; Zhu, Jing

    2015-11-01

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties.

  2. Effect of charge on the mechanical properties of surfactant bilayers.

    Science.gov (United States)

    Bradbury, Robert; Nagao, Michihiro

    2016-11-23

    Charge effects on the mechanical properties of surfactant bilayers have been measured, for a system with a low ionic strength, using small-angle neutron scattering and neutron spin echo spectroscopy. We report that, not only does increasing the surface charge density lead to greater structural ordering and a stiffening of the membrane, which is consistent with classical theory of charge effects on membranes, but also that the relaxation rate of the membrane thickness fluctuations decreases without affecting the fluctuation amplitude. From the relaxation rate we demonstrate, using recent theory, that the viscosity of the surfactant membrane is increased with surface charge density, which suggests that the amount of charge controls the diffusion behavior of inclusions inside the membrane. The present results confirm that the thickness fluctuation relaxation rate and amplitude are tuned independently since the membrane viscosity is only influencing the relaxation rate. This work demonstrates that charge stabilization of lamellar bilayers is not merely affected by intermembrane interactions and structural ordering but that intramembrane dynamics also have a significant contribution.

  3. Bi-layer functionally gradient thick film semiconducting methane sensors

    Indian Academy of Sciences (India)

    A Banerjee; A K Haldar; J Mondal; A Sen; H S Maiti

    2002-11-01

    Gas sensors based on metal oxide semiconductors like tin dioxide are widely used for the detection of toxic and combustible gases like carbon monoxide, methane and LPG. One of the problems of such sensors is their lack of sensitivity, which to some extent, can be circumvented by using different catalysts. However, highly reactive volatile organic compounds (VOC) coming from different industrial and domestic products (e.g. paints, lacquers, varnishes etc) can play havoc on such sensors and can give rise to false alarms. Any attempt to adsorb such VOCs (e.g. by using activated charcoal) results in sorption of the detecting gases (e.g. methane) too. To get round the problem, bi-layer sensors have been developed. Such tin oxide based functionally gradient bi-layer sensors have different compositions at the top and bottom layers. Here, instead of adsorbing the VOCs, they are allowed to interact and are consumed on the top layer of the sensors and a combustible gas like methane being less reactive, penetrates the top layer and interacts with the bottom layer. By modifying the chemical compositions of the top and bottom layers and by designing the electrode-lead wire arrangement properly, the top layer can be kept electrically shunted from the bottom layer and the electrical signal generated at the bottom layer from the combustible gas is collected. Such functionally gradient sensors, being very reliable, can find applications in domestic, industrial and strategic sectors.

  4. Fibonacci anyons from Abelian bilayer quantum Hall states.

    Science.gov (United States)

    Vaezi, Abolhassan; Barkeshli, Maissam

    2014-12-05

    The possibility of realizing non-Abelian statistics and utilizing it for topological quantum computation (TQC) has generated widespread interest. However, the non-Abelian statistics that can be realized in most accessible proposals is not powerful enough for universal TQC. In this Letter, we consider a simple bilayer fractional quantum Hall system with the 1/3 Laughlin state in each layer. We show that interlayer tunneling can drive a transition to an exotic non-Abelian state that contains the famous "Fibonacci" anyon, whose non-Abelian statistics is powerful enough for universal TQC. Our analysis rests on startling agreements from a variety of distinct methods, including thin torus limits, effective field theories, and coupled wire constructions. We provide evidence that the transition can be continuous, at which point the charge gap remains open while the neutral gap closes. This raises the question of whether these exotic phases may have already been realized at ν=2/3 in bilayers, as past experiments may not have definitively ruled them out.

  5. Exchange biased anisotropic magnetoresistance in Co/CoO bilayer

    Science.gov (United States)

    Sahoo, S.; Polisetty, S.; Wang, Yi; Mukherjee, T.; He, Xi; Binek, Ch.

    2008-03-01

    We measured the anisotropic magnetoresistance of a Co(11nm)/CoO bilayer in exchange biased and unbiased states. The bilayer was fabricated on a-Al2O3 substrate maintained at 300^oC by molecular beam epitaxy at a base pressure of 10-11mbar. θ-2θ X-ray diffraction scans reveal hcp (001) texture of the Co film. No peak associated with the naturally formed CoO top layer was identified. Small angle X-ray reflectivity scans yield the Co and CoO thicknesses as 11 and 2.4nm, respectively. Exchange bias was obtained from field cooled magnetoresistance measurements at various temperatures carried out in a closed cycle cryostat. Exchange bias varies quasi linearly with temperature and vanishes at the blocking temperature, TB=97K. The latter is less than 2/3 of the bulk N'eel temperature allowing to estimate the T=0 antiferromagnetic correlation length of CoO to be 1.84 nm in accordance with the geometrical confinement.

  6. Interdistance Effects on Flat and Buckled Silicene Like-bilayers

    Science.gov (United States)

    Naji, S.; Khalil, B.; Labrim, H.; Bhihi, M.; Belhaj, A.; Benyoussef, A.; Lakhal, M.; El Kenz, A.

    2014-03-01

    Using ab intio numerical calculations based on the all-electron full-potential local-orbital minimum-basis scheme FPLO9.00-34, we discuss the interdistance effect on the energy gap of two parallel layers of the silicone systems. The like- bilayer systems we dealt with here are relying on a dynamic monolayer of silicene located at distance d along the normal direction z forming with a static one a (AA) stacking arrangement. In particular, we investigate the effect of the dynamic layer by varying the distance d starting from a distance around the bond length of Van der Waals. More precisely, we consider the flat and two buckled geometries in (AA) arrangements. The flat geometry is associated with the usual (AA) configuration appearing in the pure graphene material. For buckled geometry, we can distinguish two configurations. The first one corresponds to the usual buckled configuration that keeps the same vertical distance between the two layers atoms while the remaining one is obtained by reversing one silicene layer. We show that the band gap can be opened by simply varying the distance, starting around a Van der Waals distance, between two parallel silicene for flat and buckled geometries due to an electronic transition of electrons living in pz orbital states. Furthermore, we study the stability between the buckled and the flat configuration in the mono and bilayer system.

  7. One-dimensional Topological Edge States of Bismuth Bilayers

    Science.gov (United States)

    Drozdov, Ilya; Alexandradinata, Aris; Jeon, Sangjun; Nadj-Perge, Stevan; Ji, Huiwen; Cava, Robert; Bernevig, B. Andrei; Yazdani, Ali

    2014-03-01

    The hallmark of a time-reversal symmetry protected topologically insulating state of matter in two-dimensions (2D) is the existence of chiral edge modes propagating along the perimeter of the sample. Bilayers of bismuth (Bi), an elemental system theoretically predicted to be a Quantum Spin Hall (QSH) insulator1, has been studied with Scanning Tunneling Microscopy (STM) and the electronic structure of its bulk and edge modes has been experimentally investigated. Spectroscopic mapping with STM reveals the presence of the state bound to the edges of the Bi-bilayer. By visualizing quantum interference of the edge state quasi-particles in confined geometries we characterize their dispersion and demonstrate that their properties are consistent with the absence of backscattering. Hybridization of the edge modes to the underlying substrate will be discussed. [1] Shuichi Murakami, Phys. Rev. Lett. 97, 236805 (2006). The work at Princeton and the Princeton Nanoscale Microscopy Laboratory was supported by ARO MURI program W911NF-12-1-0461, DARPA-SPWAR Meso program N6601-11-1-4110, NSF-DMR1104612, and NSF-MRSEC programs through the Princeton Center for Complex Materials (DMR-0819860)

  8. Entrenched metal lift-off using a novel bilayer process

    Science.gov (United States)

    Dubois, Thomas D.; Tranjan, Farid M.; Jones, Susan K.; Bobbio, Stephen M.; Kellam, Mark D.; Frieser, Rudolph G.; Jones, A. D.

    1990-01-01

    This paper will discuss the preparation and characterization of a modified photoresist and describe its use in a novel bilayer process. The modified photoresist solutions are prepared by dissolving enough cyclic phosphonitrilic chloride trimer, PNCT, in commercially available photoresist solutions to achieve phosphorus concentrations of 10 to 12 weight percent in the resulting films. FTNMR and FTIR data will be presented which demonstrate that the cyclic phosphonitrilic chloride trimer does not undergo chemical reaction with the components of the photoresist in the photoresist solutions or photoresist films. The exposure threshold of the PNCT modified photoresist films is 1.5 times greater than that of the unmodified films. Experimental data will be discussed which suggests the decrease in exposure threshold is the result of a relatively lower concentration of photoactive compound in the PNCT modified films. The PNCT modified films will be shown to provide resolution comparable to that of the unmodified photoresist films and yield a process window of better than 20%. A mechanism for the formation of the 02/N2 plasma resistant etch barrier formed during 02/N2 plasma etching will be discussed. Finally, a bilayer process which uses the PNCT modified photoresist in generating metal features entrenched in polyimide will be presented.

  9. Unexpected bilayer formation in Langmuir films of nucleolipids.

    Science.gov (United States)

    Desbat, Bernard; Arazam, Nessim; Khiati, Salim; Tonelli, Giovanni; Neri, Wilfrid; Barthélémy, Philippe; Navailles, Laurence

    2012-05-01

    Langmuir monolayers have been extensively investigated by various experimental techniques. These studies allowed an in-depth understanding of the molecular conformation in the layer, phase transitions, and the structure of the multilayer. As the monolayer is compressed and the surface pressure is increased beyond a critical value, usually occurring in the minimal closely packed molecular area, the monolayer fractures and/or folds, forming multilayers in a process referred to as collapse. Various mechanisms for monolayer collapse and the resulting reorganization of the film have been proposed, and only a few studies have demonstrated the formation of a bilayer after collapse and with the use of a Ca(2+) solution. In this work, Langmuir isotherms coupled with imaging ellipsometry and polarization modulation infrared reflection absorption spectroscopy were recorded to investigate the air-water interface properties of Langmuir films of anionic nucleolipids. We report for these new molecules the formation of a quasi-hexagonal packing of bilayer domains at a low compression rate, a singular behavior for lipids at the air-water interface that has not yet been documented.

  10. Interlayer thermal conductance within a phosphorene and graphene bilayer.

    Science.gov (United States)

    Hong, Yang; Zhang, Jingchao; Zeng, Xiao Cheng

    2016-11-24

    Monolayer graphene possesses unusual thermal properties, and is often considered as a prototype system for the study of thermal physics of low-dimensional electronic/thermal materials, despite the absence of a direct bandgap. Another two-dimensional (2D) atomic layered material, phosphorene, is a natural p-type semiconductor and it has attracted growing interest in recent years. When a graphene monolayer is overlaid on phosphorene, the hybrid van der Waals (vdW) bilayer becomes a potential candidate for high-performance thermal/electronic applications, owing to the combination of the direct-bandgap properties of phosphorene with the exceptional thermal properties of graphene. In this work, the interlayer thermal conductance at the phosphorene/graphene interface is systematically investigated using classical molecular dynamics (MD) simulation. The transient pump-probe heating method is employed to compute the interfacial thermal resistance (R) of the bilayer. The predicted R value at the phosphorene/graphene interface is 8.41 × 10(-8) K m(2) W(-1) at room temperature. Different external and internal conditions, i.e., temperature, contact pressure, vacancy defect, and chemical functionalization, can all effectively reduce R at the interface. Numerical results of R reduction as a function of temperature, interfacial coupling strength, defect ratio, or hydrogen coverage are reported with the most R reduction amounting to 56.5%, 70.4%, 34.8% and 84.5%, respectively.

  11. Nonlocal Drag of Magnons in a Ferromagnetic Bilayer

    Science.gov (United States)

    Liu, Tianyu; Vignale, G.; Flatté, Michael E.

    2016-06-01

    Quantized spin waves, or magnons, in a magnetic insulator are assumed to interact weakly with the surroundings, and to flow with little dissipation or drag, producing exceptionally long diffusion lengths and relaxation times. In analogy to Coulomb drag in bilayer two-dimensional electron gases, in which the contribution of the Coulomb interaction to the electric resistivity is studied by measuring the interlayer resistivity (transresistivity), we predict a nonlocal drag of magnons in a ferromagnetic bilayer structure based on semiclassical Boltzmann equations. Nonlocal magnon drag depends on magnetic dipolar interactions between the layers and manifests in the magnon current transresistivity and the magnon thermal transresistivity, whereby a magnon current in one layer induces a chemical potential gradient and/or a temperature gradient in the other layer. The largest drag effect occurs when the magnon current flows parallel to the magnetization; however, for oblique magnon currents a large transverse current of magnons emerges. We examine the effect for practical parameters, and find that the predicted induced temperature gradient is readily observable.

  12. Bilayer linearized tensor renormalization group approach for thermal tensor networks

    Science.gov (United States)

    Dong, Yong-Liang; Chen, Lei; Liu, Yun-Jing; Li, Wei

    2017-04-01

    Thermal tensor networks constitute an efficient and versatile representation for quantum lattice models at finite temperatures. By Trotter-Suzuki decomposition, one obtains a D +1 dimensional TTN for the D -dimensional quantum system and then employs efficient renormalizaton group (RG) contractions to obtain the thermodynamic properties with high precision. The linearized tensor renormalization group (LTRG) method, which can be used to contract TTN efficiently and calculate the thermodynamics, is briefly reviewed and then generalized to a bilayer form. We dub this bilayer algorithm as LTRG++ and explore its performance in both finite- and infinite-size systems, finding the numerical accuracy significantly improved compared to single-layer algorithm. Moreover, we show that the LTRG++ algorithm in an infinite-size system is in essence equivalent to transfer-matrix renormalization group method, while reformulated in a tensor network language. As an application of LTRG++, we simulate an extended fermionic Hubbard model numerically, where the phase separation phenomenon, ground-state phase diagram, as well as quantum criticality-enhanced magnetocaloric effects, are investigated.

  13. Engineering Bi-Layer Nanofibrous Conduits for Peripheral Nerve Regeneration

    Science.gov (United States)

    Zhu, Yiqian; Wang, Aijun; Patel, Shyam; Kurpinski, Kyle; Diao, Edward; Bao, Xuan; Kwong, George; Young, William L.

    2011-01-01

    Trauma injuries often cause peripheral nerve damage and disability. A goal in neural tissue engineering is to develop synthetic nerve conduits for peripheral nerve regeneration having therapeutic efficacy comparable to that of autografts. Nanofibrous conduits with aligned nanofibers have been shown to promote nerve regeneration, but current fabrication methods rely on rolling a fibrous sheet into the shape of a conduit, which results in a graft with inconsistent size and a discontinuous joint or seam. In addition, the long-term effects of nanofibrous nerve conduits, in comparison with autografts, are still unknown. Here we developed a novel one-step electrospinning process and, for the first time, fabricated a seamless bi-layer nanofibrous nerve conduit: the luminal layer having longitudinally aligned nanofibers to promote nerve regeneration, and the outer layer having randomly organized nanofibers for mechanical support. Long-term in vivo studies demonstrated that bi-layer aligned nanofibrous nerve conduits were superior to random nanofibrous conduits and had comparable therapeutic effects to autografts for nerve regeneration. In summary, we showed that the engineered nanostructure had a significant impact on neural tissue regeneration in situ. The results from this study will also lead to the scalable fabrication of engineered nanofibrous nerve conduits with designed nanostructure. This technology platform can be combined with drug delivery and cell therapies for tissue engineering. PMID:21501089

  14. Embedding Ba Monolayers and Bilayers in Boron Carbide Nanowires.

    Science.gov (United States)

    Yu, Zhiyang; Luo, Jian; Shi, Baiou; Zhao, Jiong; Harmer, Martin P; Zhu, Jing

    2015-11-26

    Aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) was employed to study the distribution of barium atoms on the surfaces and in the interiors of boron carbide based nanowires. Barium based dopants, which were used to control the crystal growth, adsorbed to the surfaces of the boron-rich crystals in the form of nanometer-thick surficial films (a type of surface complexion). During the crystal growth, these dopant-based surface complexions became embedded inside the single crystalline segments of fivefold boron-rich nanowires collectively, where they were converted to more ordered monolayer and bilayer modified complexions. Another form of bilayer complexion stabilized at stacking faults has also been identified. Numerous previous works suggested that dopants/impurities tended to segregate at the stacking faults or twinned boundaries. In contrast, our study revealed the previously-unrecognized possibility of incorporating dopants and impurities inside an otherwise perfect crystal without the association to any twin boundary or stacking fault. Moreover, we revealed the amount of barium dopants incorporated was non-equilibrium and far beyond the bulk solubility, which might lead to unique properties.

  15. Microporous bilayer osmotic tablet for colon-specific delivery.

    Science.gov (United States)

    Chaudhary, Anil; Tiwari, Neha; Jain, Vikas; Singh, Ranjit

    2011-05-01

    Microporous bilayer osmotic tablet bearing dicyclomine hydrochloride and diclofenac potassium was developed using a new oral drug delivery system for colon targeting. The tablets were coated with microporous semipermeable membrane and enteric polymer using conventional pan-coating process. The developed microporous bilayer osmotic pump tablet (OPT) did not require laser drilling to form the drug delivery orifice. The colon-specific biodegradation of pectin could form in situ delivery pores for drug release. The effect of formulation variables like inclusion of osmogen, amount of HPMC and NaCMC in core, amount of pore former in semipermeable membrane was studied. Scanning electron microscopic photographs showed formation of in situ delivery pores after predetermined time of coming in contact with dissolution medium. The number of pores was dependent on the amount of the pore former in the semipermeable membrane. In vitro dissolution results indicated that system showed acid-resistant, timed release and was able to deliver drug at an approximate zero order up to 24h. The developed tablets could be effectively used for colon-specific drug delivery to treat IBS. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. Coarse Grained Simulation of Lipid Membrane and Triblock Copolymers

    Science.gov (United States)

    Hatakeyama, Masaomi; Faller, Roland

    2008-02-01

    We investigated the interaction between DPPC (Dipalmitoyl phosphatidylcholine) bilayer and polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) triblock copolymers using coarse grained simulation. We simulated two systems of DPPC bilayer and PEO-PPO-PEO triblock copolymer containing different mole fractions, and simulated DPPC vesicle with the copolymers. We found different adsorption mechanisms of triblock copolymers depending on concentration. And we also observed docking process between a lipid vesicle and a micelle of the copolymers.

  17. Molecular dynamics simulation of the partitioning of benzocaine and phenytoin into a lipid bilayer.

    Science.gov (United States)

    Martin, Lewis J; Chao, Rebecca; Corry, Ben

    2014-01-01

    Molecular dynamics simulations were used to examine the partitioning behaviour of the local anaesthetic benzocaine and the anti-epileptic phenytoin into lipid bilayers, a factor that is critical to their mode of action. Free energy methods are used to quantify the thermodynamics of drug movement between water and octanol as well as for permeation across a POPC membrane. Both drugs are shown to favourably partition into the lipid bilayer from water and are likely to accumulate just inside the lipid headgroups where they may alter bilayer properties or interact with target proteins. Phenytoin experiences a large barrier to cross the centre of the bilayer due to less favourable energetic interactions in this less dense region of the bilayer. Remarkably, in our simulations both drugs are able to pull water into the bilayer, creating water chains that extend back to bulk, and which may modify the local bilayer properties. We find that the choice of atomic partial charges can have a significant impact on the quantitative results, meaning that careful validation of parameters for new drugs, such as performed here, should be performed prior to their use in biomolecular simulations.

  18. Studying the lateral chain packing in a ceramide bilayer with molecular dynamics simulations

    Science.gov (United States)

    Papadimitriou, N. I.; Karozis, S. N.; Kainourgiakis, M. E.; Charalambopoulou, G. Ch

    2015-01-01

    In this work, we present a novel technique, based on molecular dynamics simulations, that allows the study of the lateral chain packing in a lipid bilayer. It utilizes the radial distribution function of the alkyl chains to determine the arrangement of the chains along the bilayer plane. The positions of the mass centres of the chains are projected onto the bilayer plane and a 2D radial distribution function is calculated for these projections. The proposed technique can be particularly useful for lipid bilayers in the gel (solid) phase where the chains present a limited degree of mobility. As a case study, we have examined a bilayer that consists of ceramide NS 24:0. Ceramide bilayers can be found in the lipid domain of the skin where they have a significant role in its barrier function. The specific bilayer was found (at 300 K) to adopt a strictly hexagonal chain packing with a separation distance between the chains of 0.466 nm, in good agreement with the available experimental data.

  19. Effect of monoglyceride structure and cholesterol content on water permeability of the droplet bilayer.

    Science.gov (United States)

    Michalak, Zuzanna; Muzzio, Michelle; Milianta, Peter J; Giacomini, Rosario; Lee, Sunghee

    2013-12-23

    The process of water permeation across lipid membranes has significant implications for cellular physiology and homeostasis, and its study may lead to a greater understanding of the relationship between the structure of lipid bilayer and the role that lipid structure plays in water permeation. In this study, we formed a droplet interface bilayer (DIB) by contacting two aqueous droplets together in an immiscible solvent (squalane) containing bilayer-forming surfactant (monoglycerides). Using the DIB model, we present our results on osmotic water permeabilities and activation energy for water permeation of an associated series of unsaturated monoglycerides as the principal component of droplet bilayers, each having the same chain length but differing in the position and number of double bonds, in the absence and presence of a varying concentration of cholesterol. Our findings suggest that the tailgroup structure in a series of monoglyceride bilayers is seen to affect the permeability and activation energy for the water permeation process. Moreover, we have also established the insertion of cholesterol into the droplet bilayer, and have detected its presence via its effect on water permeability. The effect of cholesterol differs depending on the type of monoglyceride. We demonstrate that the DIB can be employed as a convenient model membrane to rapidly explore subtle structural effects on bilayer water permeability.

  20. Fluorescence of Supported Phospholipid Bilayers Recorded in a Conventional Horizontal-Beam Spectrofluorometer.

    Science.gov (United States)

    Kovrigina, Elizaveta A; Kovrigin, Evgenii L

    2016-03-01

    Supported phospholipid bilayers are a convenient model of cellular membranes in studies of membrane biophysics and protein-lipid interactions. Traditionally, supported lipid bilayers are formed on a flat surface of a glass slide to be observed through fluorescence microscopes. This paper describes a method to enable fluorescence detection from the supported lipid bilayers using standard horizontal-beam spectrofluorometers instead of the microscopes. In the proposed approach, the supported lipid bilayers are formed on the inner optical surfaces of the standard fluorescence microcell. To enable observation of the bilayer absorbed on the cell wall, the microcell is placed in a standard fluorometer cell holder and specifically oriented to expose the inner cell walls to both excitation and emission channels with a help of the custom cell adaptor. The signal intensity from supported bilayers doped with 1 % (mol) of rhodamine-labeled lipid in the standard 3-mm optical microcell was equivalent to fluorescence of the 70-80 nM reference solution of rhodamine recorded in a commercial microcell adaptor. Because no modifications to the instruments are required in this method, a variety of steady-state and time-domain fluorescence measurements of the supported phospholipid bilayers may be performed with the spectral resolution using standard horizontal-beam spectrofluorometers.

  1. Lepromatous leprosy patients produce antibodies that recognise non-bilayer lipid arrangements containing mycolic acids

    Directory of Open Access Journals (Sweden)

    Isabel Baeza

    2012-12-01

    Full Text Available Non-bilayer phospholipid arrangements are three-dimensional structures that form when anionic phospholipids with an intermediate structure of the tubular hexagonal phase II are present in a bilayer of lipids. Antibodies that recognise these arrangements have been described in patients with antiphospholipid syndrome and/or systemic lupus erythematosus and in those with preeclampsia; these antibodies have also been documented in an experimental murine model of lupus, in which they are associated with immunopathology. Here, we demonstrate the presence of antibodies against non-bilayer phospholipid arrangements containing mycolic acids in the sera of lepromatous leprosy (LL patients, but not those of healthy volunteers. The presence of antibodies that recognise these non-bilayer lipid arrangements may contribute to the hypergammaglobulinaemia observed in LL patients. We also found IgM and IgG anti-cardiolipin antibodies in 77% of the patients. This positive correlation between the anti-mycolic-non-bilayer arrangements and anti-cardiolipin antibodies suggests that both types of antibodies are produced by a common mechanism, as was demonstrated in the experimental murine model of lupus, in which there was a correlation between the anti-non-bilayer phospholipid arrangements and anti-cardiolipin antibodies. Antibodies to non-bilayer lipid arrangements may represent a previously unrecognised pathogenic mechanism in LL and the detection of these antibodies may be a tool for the early diagnosis of LL patients.

  2. Role of substrate induced electron-phonon interactions in biased graphitic bilayers

    Science.gov (United States)

    Davenport, A. R.; Hague, J. P.

    2016-08-01

    Bilayers of graphitic materials have potential applications in field effect transistors (FETs). A potential difference applied between certain ionic bilayers made from insulating graphitic materials such as BN, ZnO and AlN could reduce gap sizes, turning them into useful semiconductors. On the other hand, opening of a small semiconducting gap occurs in graphene bilayers under applied field. The aim here is to investigate to what extent substrate induced electron-phonon interactions (EPIs) modify this gap change. We examine EPIs in several lattice configurations of graphitic bilayers, using a perturbative approach. The typical effect of EPIs on the ionic bilayers is an undesirable gap widening. The size of this gap change varies considerably with lattice structure and the magnitude of the bias. When bias is larger than the non-interacting gap size, EPIs have the smallest effect on the bandgap, especially in configurations with A{{A}\\prime} and AB structures. Thus careful selection of substrate, lattice configuration and bias strength to minimise the effects of EPIs could be important for optimising the properties of electronic devices. We use parameters related to BN in this article. In practice, the results presented here are broadly applicable to other graphitic bilayers, and are likely to be qualitatively similar in metal dichalcogenide bilayers such as MoS2, which are already of high interest for their use in FETs.

  3. Comparative Study of Monolayer and Bilayer Epitaxial Graphene Field-Effect Transistors on SiC Substrates

    Institute of Scientific and Technical Information of China (English)

    Ze-Zhao He; Ke-Wu Yang; Cui Yu; Qing-Bin Liu; Jing-Jing Wang; Xu-Bo Song; Ting-Ting Han

    2016-01-01

    Monolayer and bilayer graphenes have generated tremendous excitement as the potentially useful electronic materials due to their unique features.We report on monolayer and bilayer epitaxial graphene field-effect transistors (GFETs) fabricated on SiC substrates.Compared with monolayer GFETs,the bilayer GFETs exhibit a significant improvement in dc characteristics,including increasing current density IDS,improved transconductance gm,reduced sheet resistance Ron,and current saturation.The improved electrical properties and tunable bandgap in the bilayer graphene lead to the excellent dc performance of the bilayer GFETs.Furthermore,the improved dc characteristics enhance a better rf performance for bilayer graphene devices,demonstrating that the quasifree-standing bilayer graphene on SiC substrates has a great application potential for the future graphene-based electronics.

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

    Science.gov (United States)

    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.

  5. Ghost Fano Resonance of Excitons in Twisted Bilayer Graphene

    Science.gov (United States)

    Liang, Yufeng

    2014-03-01

    Metallic systems are generally considered to be unable to harbor tightly bound excitons because of the strong screening effect as well as the absence of a finite band gap. Previously, exception has only been found in one-dimensional metallic carbon nanotubes due to the depressed screening effects and the symmetry gap. We explore the exciton spectra of twisted bilayer graphene (tBLG) and predict the existence of even more strongly bound exciton (with binding energy as large as 0.5eV) in this system despite of its higher dimensionality. Based on our results from first-principles simulations and effective model calculations, a mechanism known as the ghost Fano resonance is proposed for the bound exciton formation in metallic systems beyond the dimensonality-related argument. Our results shed light on engineering the e-h excitations in the few-layer van der Waals heterojunction. NSF Grant No. DMR-1207141.

  6. Monolayer curvature stabilizes nanoscale raft domains in mixed lipid bilayers

    CERN Document Server

    Meinhardt, Sebastian; Schmid, Friederike

    2013-01-01

    According to the lipid raft hypothesis, biological lipid membranes are laterally heterogeneous and filled with nanoscale ordered "raft" domains, which are believed to play an important role for the organization of proteins in membranes. However, the mechanisms stabilizing such small rafts are not clear, and even their existence is sometimes questioned. Here we report the observation of raft-like structures in a coarse-grained molecular model for multicomponent lipid bilayers. On small scales, our membranes demix into a liquid ordered (lo) and a liquid disordered (ld) phase. On large scales, phase separation is suppressed and gives way to a microemulsion-type state that contains nanometer size lo domains in a ld environment. Furthermore, we introduce a mechanism that generates rafts of finite size by a coupling between monolayer curvature and local composition. We show that mismatch between the spontaneous curvatures of monolayers in the lo and ld phase induces elastic interactions, which reduce the line tensi...

  7. A Bilayer Resource Model for Cloud Manufacturing Services

    Directory of Open Access Journals (Sweden)

    Linan Zhu

    2013-01-01

    Full Text Available Cloud Manufacturing and Cloud Service is currently one of the main directions of development in the manufacturing industry. Under the Cloud Manufacturing environment, the characteristics of publishing, updating, searching, and accessing manufacturing resources are massive, complex, heterogeneous, and so forth. A bilayer manufacturing resource model with separation of Cloud End and Cloud Manufacturing Platform is proposed in this paper. In Cloud End, manufacturing resources are divided into single resource and complex resource, and a basic data model of manufacturing resources oriented to enterprise interior is established to store the physical characteristics. In Cloud Manufacturing Platform, a resource service attribute model oriented to actual users is established to store the service characteristics. This model is described in detail and realized with stateful Web Service Description Language (WSDL document. An example is provided for illustrating the implementation of the concept.

  8. Superconducting properties of lithium-decorated bilayer graphene

    Science.gov (United States)

    Szczȩśniak, Dominik

    2015-07-01

    The present study provides a comprehensive theoretical analysis of the superconducting phase in selected lithium-decorated bilayer graphene nanostructures. The numerical calculations, conducted within the Eliashberg formalism, give quantitative estimations of the most important thermodynamic properties such as the critical temperature, specific heat, critical field and others. It is shown that discussed lithium-graphene systems present enhancement of their thermodynamic properties comparing to the monolayer case, e.g., the critical temperature can be raised to ∼15 \\text{K} . Furthermore, estimated characteristic thermodynamic ratios exceed predictions of the Bardeen-Cooper-Schrieffer theory suggesting that the considered lithium-graphene systems can be properly analyzed only within the strong-coupling regime.

  9. Modeling Kinetics of Distortion in Porous Bi-layered Structures

    DEFF Research Database (Denmark)

    Tadesse Molla, Tesfaye; Frandsen, Henrik Lund; Bjørk, Rasmus;

    2013-01-01

    Shape distortions during constrained sintering experiment of bi-layer porous and dense cerium gadolinium oxide (CGO) structures have been modeled. Technologies like solid oxide fuel cells require co-firing thin layers with different green densities, which often exhibit differential shrinkage...... because of different sintering rates of the materials resulting in undesired distortions of the component. An analytical model based on the continuum theory of sintering has been developed to describe the kinetics of densification and distortion in the sintering processes. A new approach is used...... to extract the material parameters controlling shape distortion through optimizing the model to experimental data of free shrinkage strains. The significant influence of weight of the sample (gravity) on the kinetics of distortion is taken in to consideration. The modeling predictions indicate good agreement...

  10. Protein-membrane interactions: blood clotting on nanoscale bilayers.

    Science.gov (United States)

    Morrissey, J H; Pureza, V; Davis-Harrison, R L; Sligar, S G; Rienstra, C M; Kijac, A Z; Ohkubo, Y Z; Tajkhorshid, E

    2009-07-01

    The clotting cascade requires the assembly of protease-cofactor complexes on membranes with exposed anionic phospholipids. Despite their importance, protein-membrane interactions in clotting remain relatively poorly understood. Calcium ions are known to induce anionic phospholipids to cluster, and we propose that clotting proteins assemble preferentially on such anionic lipid-rich microdomains. Until recently, there was no way to control the partitioning of clotting proteins into or out of specific membrane microdomains, so experimenters only knew the average contributions of phospholipids to blood clotting. The development of nanoscale membrane bilayers (Nanodiscs) has now allowed us to probe, with nanometer resolution, how local variations in phospholipid composition regulate the activity of key protease-cofactor complexes in blood clotting. Furthermore, exciting new progress in solid-state NMR and large-scale molecular dynamics simulations allow structural insights into interactions between proteins and membrane surfaces with atomic resolution.

  11. Lipid peroxidation and water penetration in lipid bilayers

    DEFF Research Database (Denmark)

    Conte, Elena; Megli, Francesco Maria; Khandelia, Himanshu

    2012-01-01

    Lipid peroxidation plays a key role in the alteration of cell membrane's properties. Here we used as model systems multilamellar vesicles (MLVs) made of the first two products in the oxidative cascade of linoleoyl lecithin, namely 1-palmitoyl-2-(13-hydroperoxy-9,11-octadecanedienoyl)-lecithin (Hp......PLPC) and 1-palmitoyl-2-(13-hydroxy-9,11-octadecanedienoyl)-lecithin (OHPLPC), exhibiting a hydroperoxide or a hydroxy group at position 13, respectively. The two oxidized lipids were used either pure or in a 1:1 molar ratio mixture with untreated 1-palmitoyl-2-linoleoyl-lecithin (PLPC). The model membranes...... were doped with spin-labeled lipids to study bilayer alterations by electron paramagnetic resonance (EPR) spectroscopy. Two different spin-labeled lipids were used, bearing the doxyl ring at position (n) 5 or 16: γ-palmitoyl-β-(n-doxylstearoyl)-lecithin (n-DSPPC) and n-doxylstearic acid (n-DSA). Small...

  12. Spin-Swapping Transport and Torques in Ultrathin Magnetic Bilayers

    KAUST Repository

    Saidaoui, Hamed Ben Mohamed

    2016-07-12

    Planar spin transport in disordered ultrathin magnetic bilayers comprising a ferromagnet and a normal metal (typically used for spin pumping, spin Seebeck and spin-orbit torque experiments) is investigated theoretically. Using a tight-binding model that puts the extrinsic spin Hall effect and spin swapping on equal footing, we show that the nature of spin-orbit coupled transport dramatically depends on the ratio between the layer thickness d and the mean free path λ. While the spin Hall effect dominates in the diffusive limit (d≫λ), spin swapping dominates in the Knudsen regime (d≲λ). A remarkable consequence is that spin swapping induces a substantial fieldlike torque in the Knudsen regime.

  13. True Bilayer Exciton Condensate of One-Dimensional Electrons

    Science.gov (United States)

    Kantian, A.; Abergel, D. S. L.

    2017-07-01

    We theoretically predict that a true bilayer exciton condensate, characterized by off-diagonal long-range order and global phase coherence, can be created in one-dimensional solid state electron systems. The mechanism by which this happens is to introduce a single particle hybridization of electron and hole populations, which locks the phase of the relevant mode and hence invalidates the Mermin-Wagner theorem. Electron-hole interactions then amplify this tendency towards off-diagonal long-range order, enhancing the condensate properties by more than an order of magnitude over the noninteracting limit. We show that the temperatures below which a substantial condensate fraction would form could reach hundreds of Kelvin, a benefit of the weak screening in one-dimensional systems.

  14. Effects of Fatty Acid Inclusion in a DMPC Bilayer Membrane

    DEFF Research Database (Denmark)

    Peters, Günther H.J.; Hansen, Flemming Yssing; Møller, Martin S.

    2009-01-01

    Free fatty acids in biomembranes have been proposed to be a central component in several cellular control and regulatory mechanisms. To elucidate some fundamental elements underlying this, we have applied molecular dynamics simulations and experimental density measurements to study the molecular...... packing and structure of oleic acid (HOA) and stearic acid (HSA) in fluid bilayers of dimyristoylphosphatidylcholine (DMPC). The experimental data show a small but consistent positive excess volume for fatty acid concentrations below 10 mol %. At higher concentrations the fatty acids mix ideally...... with fluid DMPC. The simulations, which were benchmarked against the densitometric data, revealed interesting differences in the structure and location of the fatty acids depending on their protonation status. Thus, the protonated (uncharged) acid is located rather deeply in the membrane with an average...

  15. Butterfly micro bilayer thermal energy harvester geometry with improved performances

    Science.gov (United States)

    Trioux, E.; Monfray, S.; Basrour, S.

    2016-11-01

    This paper reports the recent progress of a new technology to scavenge thermal energy, implying a double-step transduction through thermal buckling of a bilayer aluminum nitride / aluminum bridge and piezoelectric transduction. A completely new scavenger design is presented, improving greatly its final performance. The butterfly shape reduces the overall device mechanical rigidity, which leads to a decrease of buckling temperatures compared to previously studied rectangular plates. In a first time we compared performances of rectangular and butterfly plates with an equal thickness of Al and AlN. In a second time, with a thicker Al layer than AlN layer, we will study only butterfly structure in terms of output power and buckling temperatures, and compare it to the previous stack.

  16. Spin-Swapping Transport and Torques in Ultrathin Magnetic Bilayers

    Science.gov (United States)

    Saidaoui, Hamed Ben Mohamed; Manchon, A.

    2016-07-01

    Planar spin transport in disordered ultrathin magnetic bilayers comprising a ferromagnet and a normal metal (typically used for spin pumping, spin Seebeck and spin-orbit torque experiments) is investigated theoretically. Using a tight-binding model that puts the extrinsic spin Hall effect and spin swapping on equal footing, we show that the nature of spin-orbit coupled transport dramatically depends on the ratio between the layer thickness d and the mean free path λ . While the spin Hall effect dominates in the diffusive limit (d ≫λ ), spin swapping dominates in the Knudsen regime (d ≲λ ). A remarkable consequence is that spin swapping induces a substantial fieldlike torque in the Knudsen regime.

  17. Topological states in two-dimensional hexagon lattice bilayers

    Science.gov (United States)

    Zhang, Ming-Ming; Xu, Lei; Zhang, Jun

    2016-10-01

    We investigate the topological states of the two-dimensional hexagon lattice bilayer. The system exhibits a quantum valley Hall (QVH) state when the interlayer interaction t⊥ is smaller than the nearest neighbor hopping energy t, and then translates to a trivial band insulator state when t⊥ / t > 1. Interestingly, the system is found to be a single-edge QVH state with t⊥ / t = 1. The topological phase transition also can be presented via changing bias voltage and sublattice potential in the system. The QVH states have different edge modes carrying valley current but no net charge current. The bias voltage and external electric field can be tuned easily in experiments, so the present results will provide potential application in valleytronics based on the two-dimensional hexagon lattice.

  18. Lipid Bilayer Composition Affects Transmembrane Protein Orientation and Function

    Directory of Open Access Journals (Sweden)

    Katie D. Hickey

    2011-01-01

    Full Text Available Sperm membranes change in structure and composition upon ejaculation to undergo capacitation, a molecular transformation which enables spermatozoa to undergo the acrosome reaction and be capable of fertilization. Changes to the membrane environment including lipid composition, specifically lipid microdomains, may be responsible for enabling capacitation. To study the effect of lipid environment on proteins, liposomes were created using lipids extracted from bull sperm membranes, with or without a protein (Na+ K+-ATPase or -amylase. Protein incorporation, function, and orientation were determined. Fluorescence resonance energy transfer (FRET confirmed protein inclusion in the lipid bilayer, and protein function was confirmed using a colourometric assay of phosphate production from ATP cleavage. In the native lipid liposomes, ATPase was oriented with the subunit facing the outer leaflet, while changing the lipid composition to 50% native lipids and 50% exogenous lipids significantly altered this orientation of Na+ K+-ATPase within the membranes.

  19. The enhancement of vortex pinning in ferromagnet/superconductor bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Cieplak, Marta Z.; Adamus, Z.; Abal' oshev, A.; Abal' osheva, I.; Berkowski, M. [Polish Academy of Sciences, Al. Lotnikw 32/46, 02668 Warsaw (Poland); Cheng, X.M.; Sang, Hai; Chien, C.L. [Department of Physics and Astronomy, The Johns Hopkins University, Baltimore, Md 21218 (United States)

    2005-03-01

    The magnetic-domain induced vortex pinning is studied in the ferromagnet/superconductor bilayers (FSB's), in which the F layers are Co/Pt multilayers with perpendicular magnetic anisotropy, and the S layers are either niobium or high temperature superconductor YBa{sub 2}Cu{sub 3}O{sub 7} (YBCO). The magnetization measurements reveal the enhancement of the flux pinning in both types of FSB's during the reversal of the magnetization of the F layer, but the details of the behavior depend on the type of the S layer. In the case of niobium FSB the maximum of pinning appears when the F layer is in the final stage of the magnetic reversal process, while the FSB with YBCO shows the maximum when the F layer is saturated. The possible origins of these differences are discussed. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  20. Magnetic bilayer-skyrmions without skyrmion Hall effect

    Science.gov (United States)

    Zhang, Xichao; Zhou, Yan; Ezawa, Motohiko

    2016-01-01

    Magnetic skyrmions might be used as information carriers in future advanced memories, logic gates and computing devices. However, there exists an obstacle known as the skyrmion Hall effect (SkHE), that is, the skyrmion trajectories bend away from the driving current direction due to the Magnus force. Consequently, the skyrmions in constricted geometries may be destroyed by touching the sample edges. Here we theoretically propose that the SkHE can be suppressed in the antiferromagnetically exchange-coupled bilayer system, since the Magnus forces in the top and bottom layers are exactly cancelled. We show that such a pair of SkHE-free magnetic skyrmions can be nucleated and be driven by the current-induced torque. Our proposal provides a promising means to move magnetic skyrmions in a perfectly straight trajectory in ultra-dense devices with ultra-fast processing speed.

  1. Stacking transition in bilayer graphene caused by thermally activated rotation

    Science.gov (United States)

    Zhu, Mengjian; Ghazaryan, Davit; Son, Seok-Kyun; Woods, Colin R.; Misra, Abhishek; He, Lin; Taniguchi, Takashi; Watanabe, Kenji; Novoselov, Kostya S.; Cao, Yang; Mishchenko, Artem

    2017-03-01

    Crystallographic alignment between two-dimensional crystals in van der Waals heterostructures brought a number of profound physical phenomena, including observation of Hofstadter butterfly and topological currents, and promising novel applications, such as resonant tunnelling transistors. Here, by probing the electronic density of states in graphene using graphene-hexagonal boron nitride-graphene tunnelling transistors, we demonstrate a structural transition of bilayer graphene from incommensurate twisted stacking state into a commensurate AB stacking due to a macroscopic graphene self-rotation. This structural transition is accompanied by a topological transition in the reciprocal space and by pseudospin texturing. The stacking transition is driven by van der Waals interaction energy of the two graphene layers and is thermally activated by unpinning the microscopic chemical adsorbents which are then removed by the self-cleaning of graphene.

  2. Theoretical studies of lipid bilayer electroporation using molecular dynamics simulations

    Science.gov (United States)

    Levine, Zachary Alan

    Computer simulations of physical, chemical, and biological systems have improved tremendously over the past five decades. From simple studies of liquid argon in the 1960s to fully atomistic simulations of entire viruses in the past few years, recent advances in high-performance computing have continuously enabled simulations to bridge the gap between scientific theory and experiment. Molecular dynamics simulations in particular have allowed for the direct observation of spatial and temporal events which are at present inaccessible to experiments. For this dissertation I employ all-atom molecular dynamics simulations to study the transient, electric field-induced poration (or electroporation) of phospholipid bilayers at MV/m electric fields. Phospholipid bilayers are the dominant constituents of cell membranes and act as both a barrier and gatekeeper to the cell interior. This makes their structural integrity and susceptibility to external perturbations an important topic for study, especially as the density of electromagnetic radiation in our environment is increasing steadily. The primary goal of this dissertation is to understand the specific physical and biological mechanisms which facilitate electroporation, and to connect our simulated observations to experiments with live cells and to continuum models which seek to describe the underlying biological processes of electroporation. In Chapter 1 I begin with a brief introduction to phospholipids and phospholipid bilayers, followed by an extensive overview of electroporation and atomistic molecular dynamics simulations. The following chapters will then focus on peer-reviewed and published work we performed, or on existing projects which are currently being prepared for submission. Chapter 2 looks at how external electric fields affect both oxidized and unoxidized lipid bilayers as a function of oxidation concentration and oxidized lipid type. Oxidative damage to cell membranes represents a physiologically relevant

  3. Thickness dependence of the exchange bias in epitaxial manganite bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Kobrinskii, A. L. [University of Minnesota; Goldman, A. M. [University of Minnesota; Varela del Arco, Maria [ORNL

    2009-01-01

    Exchange bias has been studied in a series of La{sub 2/3}Ca{sub 1/3}MnO{sub 3}/La{sub 1/3}Ca{sub 2/3}MnO{sub 3} bilayers grown on (001) SrTiO{sub 3} substrates by ozone-assisted molecular-beam epitaxy. The high crystalline quality of the samples and interfaces has been verified using high-resolution x-ray diffractometry and Z-contrast scanning transmission electron microscopy with electron-energy-loss spectroscopy. The dependence of exchange bias on the thickness of the antiferromagnetic layer has been investigated. A critical value for the onset of the hysteresis loop shift has been determined. An antiferromagnetic anisotropy constant has been obtained by fitting the results to the generalized Meiklejohn-Bean model.

  4. Thickness dependence of the exchange bias in epitaxial manganite bilayers

    Science.gov (United States)

    Kobrinskii, A. L.; Goldman, A. M.; Varela, Maria; Pennycook, S. J.

    2009-03-01

    Exchange bias has been studied in a series of La2/3Ca1/3MnO3/La1/3Ca2/3MnO3 bilayers grown on (001) SrTiO3 substrates by ozone-assisted molecular-beam epitaxy. The high crystalline quality of the samples and interfaces has been verified using high-resolution x-ray diffractometry and Z -contrast scanning transmission electron microscopy with electron-energy-loss spectroscopy. The dependence of exchange bias on the thickness of the antiferromagnetic layer has been investigated. A critical value for the onset of the hysteresis loop shift has been determined. An antiferromagnetic anisotropy constant has been obtained by fitting the results to the generalized Meiklejohn-Bean model.

  5. Protein-induced bilayer Perturbations: Lipid ordering and hydrophobic coupling

    DEFF Research Database (Denmark)

    Petersen, Frederic Nicolas Rønne; Laursen, Ib; Bohr, Henrik;

    2009-01-01

    The host lipid bilayer is increasingly being recognized as an important non-specific regulator of membrane protein function. Despite considerable progress the interplay between hydrophobic coupling and lipid ordering is still elusive. We use electron spin resonance (ESR) to study the interaction...... and hydrophobic mismatch. Our findings also show that at high protein:lipid ratios the lipids are motionally restricted but not completely immobilized. Both exchange on and off rate values for the lipid ↔ gramicidin interaction are lowest at optimal hydrophobic matching. Hydrophobic mismatch of few Å results...... in up to 10-fold increased exchange rates as compared to the ‘optimal’ match situation pointing to the regulatory role of hydrophobic coupling in lipid–protein interactions....

  6. Resonant tunnelling in a Fibonacci bilayer graphene superlattice

    Energy Technology Data Exchange (ETDEWEB)

    Mukhopadhyay, S.; Sinha, C. [Department of Theoretical Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, West Bengal (India); Biswas, R. [Department of Physics, PK College, Contai, Purba Medinipur, West Bengal (India)

    2010-02-15

    The transmission coefficients (TCs) and angularly averaged conductance for quasi-particle transport are studied for a bilayer graphene superlattice arranged according to the Fibonacci sequence. The transmission is found to be symmetric around the superlattice growth direction and highly sensitive to the direction of the quasi-particle incidence. The transmission spectra are fragmented and appear in groups due to the quasi-periodicity of the system. The average conductance shows interesting structures sharply dependent on the height of the potential barriers between two graphene strips. The low-energy conductance due to Klein transmission is substantially modified by the inclusion of quasi-periodicity in the system. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  7. Phosphatidyl-hydroxytyrosol and phosphatidyl-tyrosol bilayer properties.

    Science.gov (United States)

    Evans, Kervin O; Compton, David L

    2017-01-01

    Hydroxytyrosol and tyrosol phospholipids were enzymatically synthesized and investigated for their bilayer properties. Dynamic light scattering demonstrated that hand extrusion at 100nm consistently resulted in liposomes of nearly 85nm diameter for both phosphatidyl-hydroxytyrosol (DOPHT) and phosphatidyl-tyrosol (DOPT). Transmission electron microscopy showed DOPT and DOPHT liposomes extruded at 100-nm to be spherical and non-distinctive from one another. Zeta potential measurements resulted in surface charges<-25mV, demonstrating both DOPT and DOPHT form highly stable liposomes. Quartz crystal microbalance with dissipation monitoring measurements demonstrated that liposomal adsorption was dependent on a combination of DOPT (or DOPHT) mole-percent and calcium ions concentration. Fluorescence anisotropy measurements indicated that melting temperatures of DOPT and DOPHT were below 4°C, suggesting that adsorption behavior and liposome formation was limited by electrostatic interactions and not gel-state formation.

  8. Bilayer fractal structure with multiband left-handed characteristics.

    Science.gov (United States)

    Du, Qiujiao; Liu, Jinsong; Yang, Hongwu; Yi, Xunong

    2011-08-20

    We present a bilayer fractal structure for the realization of multiband left-handed metamaterial at terahertz frequencies. The structure is composed of metallic H-fractal pairs separated by a dielectric layer. The electromagnetic properties of periodic H-fractal pairs have been investigated by numerical simulation. The period in the propagation direction is extremely small as compared to the wavelength at the operational frequency. Under the electromagnetic wave normal incidence, the material exhibits negative refraction simultaneously around the frequencies of 0.10 and 0.15 THz for parallel polarization, and around the frequencies of 0.19 and 0.38 THz for perpendicular polarization. The design provides a left-handed metamaterial suitable for multiband and compact devices at terahertz frequencies.

  9. Addressing Raman features of individual layers in isotopically labeled Bernal stacked bilayer graphene

    Science.gov (United States)

    Costa, Sara D.; Weis, Johan Ek; Frank, Otakar; Fridrichová, Michaela; Kalbac, Martin

    2016-06-01

    In this report important Raman modes for the evaluation of strain in graphene (the 2D and 2D‧) are analyzed. The isotope labeling is used to disentangle contribution of individual graphene layers of graphene bilayer to the studied Raman modes. It is shown that for Bernal-stacked bilayers, the 2D and the 2D‧ Raman modes have three distinct components that can be assigned to processes originating solely from the top graphene layer, bottom graphene layer, and from a combination of processes originating both from the top and bottom layers. The reported results thus enable addressing the properties of individual graphene layers in graphene bilayer by Raman spectroscopy.

  10. The interaction of new piroxicam analogues with lipid bilayers--a calorimetric and fluorescence spectroscopic study.

    Science.gov (United States)

    Maniewska, Jadwiga; Szczęśniak-Sięga, Berenika; Poła, Andrzej; Sroda-Pomianek, Kamila; Malinka, Wiesław; Michalak, Krystyna

    2014-01-01

    The purpose of the present paper was to assess the ability of new piroxicam analogues to interact with the lipid bilayers. The results of calorimetric and fluorescence spectroscopic experiments of two new synthesized analogues of piroxicam, named PR17 and PR18 on the phase behavior of phospholipid bilayers and fluorescence quenching of fluorescent probes (Laurdan and Prodan), which molecular location within membranes is known with certainty, are shown in present work. The presented results revealed that, depending on the details of chemical structure, the studied compounds penetrated the lipid bilayers.

  11. Failure modes and fracture origins of porcelain veneers on bilayer dental crowns.

    Science.gov (United States)

    Liu, Yihong; Liu, Guanghua; Wang, Yong; Shen, James Zhijian; Feng, Hailan

    2014-01-01

    The aims of this study were to determine the fracture origins and crack paths in the porcelain of clinically failed bilayer ceramic restorations and to reveal the correlation between the porcelain failures and material properties. Three clinically failed crowns of each material (bilayer zirconia crowns, galvano-ceramic crowns, and porcelain-fused-to-metal crowns) were collected and underwent failure analysis. The fractures found in porcelain veneers showed several characteristics including wear, Hertzian cone crack, chipping off, and delamination. The results indicated that the fracture origins and features of the porcelain in bilayer ceramic restorations might be affected by the rigidity of core materials and thickness of copings.

  12. Phase Transition of MoS2 Bilayer Structures

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Bothra, Pallavi; Pati, Swapan K.

    2016-01-01

    In the present study, using density functional calculations we have investigated a possible mechanism for the structural phase transition of the semiconducting bilayer 2H-MoS2 via lithiation. The results indicate that the addition of lithium to the bilayer 2H-MoS2 transforms the bilayer to a hete...... microscopic mechanism of the phase transition in MoS2 and enriches the atomic scale understanding of the interaction of MoS2 with the alkali ions and other transition metal dichalcogenides manifesting a similar phase transition....

  13. Hexagonal-shaped monolayer-bilayer quantum disks in graphene: A tight-binding approach

    Science.gov (United States)

    da Costa, D. R.; Zarenia, M.; Chaves, Andrey; Pereira, J. M.; Farias, G. A.; Peeters, F. M.

    2016-07-01

    Using the tight-binding approach, we investigate confined states in two different hybrid monolayer-bilayer systems: (i) a hexagonal monolayer area surrounded by bilayer graphene in the presence of a perpendicularly applied electric field and (ii) a hexagonal bilayer graphene dot surrounded by monolayer graphene. The dependence of the energy levels on dot size and external magnetic field is calculated. We find that the energy spectrum for quantum dots with zigzag edges consists of states inside the gap which range from dot-localized states, edge states, to mixed states coexisting together, whereas for dots with armchair edges, only dot-localized states are observed.

  14. Hydroxytyrosol and tyrosol esters partitioning into, location within, and effect on DOPC liposome bilayer behavior.

    Science.gov (United States)

    Evans, Kervin O; Laszlo, Joseph A; Compton, David L

    2015-05-01

    The phenols hydroxytyrosol and tyrosol made abundantly available through olive oil processing were enzymatically transesterified into effective lipophilic antioxidants with cuphea oil. The hydroxytyrosyl and tyrosyl esters made from cuphea oil were assessed for their ability to partition into, locate within and effect the bilayer behavior of 1,2-dioloeoylphosphatidylcholine liposomes and compared to their counterparts made from decanoic acid. Partitioning into liposomes was on the same scale for both hydroxytyrosyl derivatives and both tyrosyl derivatives. All were found to locate nearly at the same depth within the bilayer. Each was found to affect bilayer behavior in a distinct manner.

  15. Hydrocarbon chain conformation in an intercalated surfactant monolayer and bilayer

    Indian Academy of Sciences (India)

    N V Venkataraman; S Vasudevan

    2001-10-01

    Cetyl trimethyl ammonium (CTA) ions have been confined within galleries of layered CdPS3 at two different grafting densities. Low grafting densities are obtained on direct intercalation of CTA ions into CdPS3 to give Cd0.93PS3(CTA)0.14. Intercalation occurs with a lattice expansion of 4.8 Å with the interlamellar surfactant ion lying flat forming a monolayer. Intercalation at higher grafting densities was effected by a two-step ion-exchange process to give Cd0.83PS3(CTA)0.34, with a lattice expansion of 26.5 Å. At higher grafting densities the interlamellar surfactant ions adopt a tilted bilayer structure. 13C NMR and orientation-dependent IR vibrational spectroscopy on single crystals have been used to probe the conformation and orientation of the methylene ‘tail’ of the intercalated surfactant in the two phases. In the monolayer phase, the confined methylene chain adopts an essentially all-trans conformation with most of the trans chain aligned parallel to the gallery walls. On lowering the temperature, molecular plane aligns parallel, so that the methylene chain lies flat, rigid and aligned to the confining surface. In the bilayer phase, most bonds in the methylene chain are in trans conformation. It is possible to identify specific conformational sequences containing a gauche bond, in the interior and termini of the intercalated methylene. These high energy conformers disappear on cooling leaving all fifteen methylene units of the intercalated cetyl trimethyl ammonium ion in trans conformational registry at 40 K.

  16. Optical and electrical properties of bi-layers organic devices

    Science.gov (United States)

    Trad, Hager; Rouis, Ahlem; Davenas, Jöel; Majdoub, Mustapha

    2014-10-01

    The influence of interfacial charges on the device characteristics of bi-layers structure LEDs with poly[5-methoxy-2-octyloxy-1,4-phenylenevinylene] (MO-PPV) as active polymer layer is investigated. The concept to improve device performance is presented using: a diacetate cellulose (DAC) and a new synthetized 5-{2-(2-chloroethoxy)ethoxy}-2-{(E)-(2-pyridyl)azo}phenol (PDEG) components. The DAC and mixed (DAC+PDEG) layers were inserted between indium tin oxide (ITO) and MO-PPV polymer. The optical properties (UV-Vis) of MO-PPV, PDEG and mixed (DAC+PDEG) in solutions were studied and compared to those on thin films. Detailed current-voltage measurements of the bi-layers devices showed improvements of the threshold voltage (Vth) of the ITO/(DAC+PDEG)/MO-PPV/Al device attributed to the enhancement of carriers injection and transport resulted from the modified electrode structures. Conduction mechanisms of structure LEDs were matched with space-charge-limited current (SCLC) one. The impedance spectra for all devices can be discussed in terms of an equivalent circuit model designed as a parallel resistor Rp and capacitor Cp network in series with resistor Rs. The ITO/(DAC+PDEG)/MO-PPV/Al device showed the lowest impedance attributed to the removal of contaminants and to changes in the work function of ITO. The frequency-dependent electrical properties of the ITO/(DAC+PDEG)/MO-PPV/Al structure is analyzed by impedance spectroscopy as function of bias. We have extracted numerical values of the equivalent circuit model parameters by fitting experimental data. Their evolution with bias voltages has shown that the SCLC mechanism is characterized by an exponential trap distribution.

  17. Boundary potential of lipid bilayers: methods and interpretations

    Science.gov (United States)

    Ermakov, Yu A.; Nesterenko, A. M.

    2017-01-01

    The electric field distribution at the boundaries of cell membrane consists of diffuse part of the electrical double layer and the potential drop over polar area inside the membrane itself. The latter is generally attributed to the dipole effect, which depends on the lipid hydration and phase state. This report focuses on the experimental approaches developed to detect the relation between dipole effects and the bilayer structure, and to study their molecular nature. The total boundary potential (BP) of planar bilayer lipid membranes (BLM) can be controlled by Intramembranous Field Compensation (IFC) method developed in our laboratory. When combined with electrokinetic measurements in liposome suspension it allows detecting the changes of the dipole potential due to adsorption of inorganic cations and charged molecules. Multivalent inorganic cations increase the dipole potential up to 100-150 mV and make the membrane rigid. Most of these observations were simulated by Molecular Dynamics (MD) in order to visualize the relationship of electric field with the different structural factors (lipid structure, water orientation, ion adsorption etc.) responsible for its dipole component. Two principal contributors to BP – water and lipid molecules – create the opposite effects. The negative contribution with respect to the bulk is due to lipid itself and the inorganic cation penetration into the polar area of membrane. The positive contribution is caused by water orientation. Particularly, in the case of lysine adsorption, the contribution of water includes the rearrangement of H-bonds with the lipid phosphate group. This fact explains well the unusual kinetic phenomena registered by IFC in the case of polylysine adsorption at the BLM surface.

  18. Permeability of lipid bilayers to amino acids and phosphate

    Science.gov (United States)

    Chakrabarti, A. C.; Deamer, D. W.

    1992-01-01

    Permeability coefficients for amino acid classes, including neutral, polar, hydrophobic, and charged species, were measured and compared with values for other ionic solutes such as phosphate. The rates of efflux of glycine, lysine, phenylalanine, serine and tryptophan were determined after they were passively entrapped in large unilamellar vesicles (LUVs) composed of egg phosphatidylcholine (EPC) or dimyristoylphosphatidylcholine (DMPC). The following permeability coefficients were obtained for: glycine, 5.7 x 10(-12) cm s-1 (EPC), 2.0 x 10(-11) cm s-1 (DMPC); serine, 5.5 x 10(-12) cm s-1 (EPC), 1.6 x 10(-11) cm s-1 (DMPC); lysine, 5.1 x 10(-12) cm s-1 (EPC), 1.9 x 10(-11) cm s-1 (DMPC); tryptophan, 4.1 x 10(-10) cm s-1 (EPC); and phenylalanine, 2.5 x 10(-10) cm s-1 (EPC). Decreasing lipid chain length increased permeability slightly, while variations in pH had only minor effects on the permeability coefficients of the amino acids tested. Phosphate permeability was in the range of 10(-12)-10(-13) cm s-1 depending on the pH of the medium. The values for the polar and charged amino acids were surprisingly similar to those previously measured for monovalent cations such as sodium and potassium, which are in the range of 10(-12)-10(-13) cm s-1, depending on conditions and the lipid species used. This observation suggests that the permeation rates for the neutral, polar and charged amino acids are controlled by bilayer fluctuations and transient defects, rather than partition coefficients and Born energy barriers. The results are relevant to the permeation of certain peptides into lipid bilayers during protein translocation and membrane biogenesis.

  19. Analysis of tempering stresses in bilayered porcelain discs.

    Science.gov (United States)

    DeHoff, P H; Anusavice, K J

    1992-05-01

    Previous studies of opaque-porcelain/body-porcelain discs have shown that compressive stresses which develop in the porcelain surface by being tempered in air can inhibit the sizes of cracks induced within the surface. The objective of this study was to develop a theoretical model for analysis of transient and residual stresses in opaque-porcelain/body-porcelain discs which were produced under variable cooling conditions. The model incorporates the effects of stress and structural relaxation. Transient and residual stresses were calculated for bilayered porcelain discs 16 mm in diameter and 2 mm in thickness for three opaque-porcelain/body-porcelain combinations. Transient temperature distributions in the discs for simulated convective cooling were calculated by finite-element analysis. Data from microhardness indentations reported by Anusavice et al. (1989) indicate that crack lengths measured for bilayered porcelain discs subjected to slow cooling conditions, for which the model predicted residual tensile stresses, were greater than those combinations for which residual compressive stresses were calculated. Calculated values of residual compressive stress for tempered specimens were considerably higher than those for specimens that were slowly cooled and those that were cooled by free convection. In general, residual stress levels calculated by use of the analytical model were in fairly good agreement with the trends observed for crack lengths and bi-axial flexural strengths reported by Anusavice and Hojjatie (1991). The results of the present study indicate that a visco-elastic model is a viable approach for determination of transient and residual stresses in opaque-porcelain/body-porcelain discs.

  20. Electric gating induced bandgaps and enhanced Seebeck effect in zigzag bilayer graphene ribbons

    Science.gov (United States)

    Vu, Thanh-Tra; Tran, Van-Truong

    2016-08-01

    We theoretically investigate the effect of a transverse electric field generated by side gates and a vertical electric field generated by top/back gates on energy bands and transport properties of zigzag bilayer graphene ribbons (Bernal stacking). Using atomistic tight binding calculations and Green’s function formalism we demonstrate that a bandgap is opened when either field is applied and even enlarged under simultaneous influence of the two fields. Interestingly, although vertical electric fields are widely used to control the bandgap in bilayer graphene, here we show that transverse fields exhibit a more positive effect in terms of modulating a larger range of bandgap and retaining good electrical conductance. The Seebeck effect is also demonstrated to be enhanced strongly—by about 13 times for a zigzag bilayer graphene ribbon with 16 chain lines. These results may motivate new designs of devices made of bilayer graphene ribbons using electric gates.