Impact of monoolein on aquaporin1-based supported lipid bilayer membranes

Abstract

Aquaporin (AQP) based biomimetic membranes have attracted considerable attention for their potential water purification applications. In this paper, AQP1 incorporated biomimetic membranes were prepared and characterized. The morphology and structure of the biomimetic membranes were characterized by in situ atomic force microscopy (AFM), infrared absorption spectroscopy, fluorescence microscopy, and contact angle measurements. The nanofiltration performance of the AQP1 incorporated membranes was investigated at 4 bar by using 2 g l^?1 NaCl as feed solution. Lipid mobility plays an important role in the performance of the AQP1 incorporated supported lipid bilayer (SLB) membranes. We demonstrated that the lipid mobility is successfully tuned by the addition of monoolein (MO). Through in situ AFM and fluorescence recovery after photo-bleaching (FRAP) measurements, the membrane morphology and the molecular mobility were studied. The lipid mobility increased in the sequence DPPC < DPPC/MO (R_MO = 5/5) < DOPC/MO (R_MO = 5/5) < DOPC, which is consistent with the flux increment and salt rejection. This study may provide some useful insights for improving the water purification performance of biomimetic membranes.     

One-step route to a hybrid TiO2/TixW1?xN nanocomposite by in situ selective carbothermal nitridation

Metal oxide/nitride nanocomposites have many existing and potential applications, e.g. in energy conversion or ammonia synthesis. Here, a hybrid oxide/nitride nanocomposite (anatase/Ti_xW_1−xN) was synthesized by an ammonia-free sol–gel route. Synchrotron x-ray diffraction, complemented with electron microscopy and thermogravimetric analysis, was used to study the structure, composition and mechanism of formation of the nanocomposite. The nanocomposite contained nanoparticles (<5 nm diameter) of two highly intermixed phases. This was found to arise from controlled nucleation and growth of a single oxide intermediate from the gel precursor, followed by phase separation and in situ selective carbothermal nitridation. Depending on the preparation conditions, the composition varied from anatase/Ti_xW_1−xN at low W content to an isostructural mixture of Ti-rich and W-rich Ti_xW_1−xN at high W content. In situ selective carbothermal nitridation offers a facile route to the synthesis of nitride-oxide nanocomposites. This conceptually new approach is a significant advance from previous methods, which generally require ammonolysis of a pre-synthesized oxide.     

Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air–water interface

Phospholipid monomolecular films at the air–water interface are useful model membranes to understand miscibility among various components. Surface pressure (π)–area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)–dipalmitoylphosphatidylcholine (DPPC) and DoTAP–dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous π–A isotherm. Associative interactions were identified in DPPC–DoTAP mixtures compared to the pure components, while DPPG–DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC–DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X_DoTAP values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC–DoTAP mixtures with increasing X_DoTAP. However, DPPG–DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.     

Concentration dependence of lipopolymer self-diffusion in supported bilayer membranes

Self-diffusion coefficients of poly(ethylene glycol)2k-derivatized lipids (DSPE-PEG2k-CF) in glass-supported DOPC phospholipid bilayers are ascertained from quantitative fluorescence recovery after photobleaching (FRAP). We developed a first-order reaction–diffusion model to ascertain the bleaching constant, mobile fraction and lipopolymer self-diffusion coefficient D_s at concentrations in the range c ≈ 0.5–5 mol%. In contrast to control experiments with 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-(7-nitro-2-1,3-benzoxadiazol-4-yl) (ammonium salt) (DOPE-NBD) in 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), the lipopolymer self-diffusion coefficient decreases monotonically with increasing concentration, without a distinguishing mushroom-to-brush transition. Our data yield a correlation D_s = D₀/(1 + αc), where D₀ ≈ 3.36 µm² s⁻¹ and α ≈ 0.56 (with c expressed as a mole percent). Interpreting the dilute limit with the Scalettar–Abney–Owicki statistical mechanical theory for transmembrane proteins yields an effective disc radius a_e ≈ 2.41 nm. On the other hand, the Bussell–Koch–Hammer theory, which includes hydrodynamic interactions, yields a_e ≈ 2.92 nm. As expected, both measures are smaller than the Flory radius of the 2 kDa poly(ethylene glycol) (PEG) chains, R_F ≈ 3.83 nm, and significantly larger than the nominal radius of the phospholipid heads, a_l ≈ 0.46 nm. The diffusion coefficient at infinite dilution D₀ was interpreted using the Evans–Sackmann theory, furnishing an inter-leaflet frictional drag coefficient b_s ≈ 1.33 × 10⁸ N s m⁻³. Our results suggest that lipopolymer interactions are dominated by the excluded volume of the PEG-chain segments, with frictional drag dominated by the two-dimensional bilayer hydrodynamics.     

Electrochemical, atomic force microscopy and infrared reflection absorption spectroscopy studies of pre-formed mussel adhesive protein films on carbon steel for corrosion protection

Electrochemical measurements, in situ and ex situ atomic force microscopy (AFM) experiments and infrared reflection absorption spectroscopy (IRAS) analysis were performed to investigate the formation and stability as well as corrosion protection properties of mussel adhesive protein (Mefp-1) films on carbon steel, and the influence of cross-linking by NaIO₄ oxidation. The in situ AFM measurements show flake-like adsorbed protein aggregates in the film formed at pH 9. The ex situ AFM images indicate multilayer-like films and that the film becomes more compact and stable in NaCl solution after the cross-linking. The IRAS results reveal the absorption bands of Mefp-1 on carbon steel before and after NaIO₄ induced oxidation of the pre-adsorbed protein. Within a short exposure time, a certain corrosion protection effect was noted for the pre-formed Mefp-1 film in 0.1 M NaCl solution. Cross-linking the pre-adsorbed film by NaIO₄ oxidation significantly enhanced the protection efficiency by up to 80%.     

Effect of bovine serum albumin on the functionality and structure of catanionic surfactant at air–buffer interface

Interaction of bovine serum albumin (BSA) with the solvent spread monolayer of a catanionic surfactant, octadecyltrimethylammonium dodecylsulfate, (C₁₈TA⁺DS^?) at the air–buffer interface was investigated by measuring the surface pressure with time and change in surface area. Dipalmitoylphosphatidylcholine (DPPC) was used as reference. Kinetics of BSA desorption from the interface to the buffer subphase, that of C₁₈TA⁺DS^? and DPPC through their interaction with BSA, were also studied at different BSA concentrations (in the subphase) and surface pressures. Surface pressure (π)–area (A) isotherms (at pH = 5.4, μ = 0.01, T = 298 K) revealed that the coacervate/DPPC monolayer becomes expanded in the presence of BSA at low π while their protein bound species are released into the subphase at high π. Film morphology, studied by epifluorescence microscopy (EFM) and atomic force microscopy (AFM), reveals that the sizes of the domains of both DPPC and coacervate decrease in the presence of BSA. Presence of BSA in the coacervate and DPPC monolayer was supported from AFM data analysis.     

Graphene oxide‐ellagic acid nanocomposite as effective anticancer and antimicrobial agent

In this study, ellagic acid (ELA), a skin anticancer drug, is capped on the surface(s) of functionalised graphene oxide (GO) nano‐sheets through electrostatic and π–π staking interactions. The prepared ELA‐GO nanocomposite have been thoroughly characterised by using eight techniques: Fourier‐transform infrared spectroscopy (FTIR), zeta potential, X‐ray diffraction (XRD), thermogravimetric analysis (TGA), Raman spectroscopy, atomic force microscopy (AFM) topographic imaging, transmission electron microscopy (TEM), and surface morphology via scanning electron microscopy (SEM). Furthermore, ELA drug loading and release behaviours from ELA‐GO nanocomposite were studied. The ELA‐GO nanocomposite has a uniform size distribution averaging 88 nm and high drug loading capacity of 30 wt.%. The in vitro drug release behaviour of ELA from the nanocomposite was investigated by UV–Vis spectrometry at a wavelength of λ _max 257 nm. The data confirmed prolonged ELA release over 5000 min at physiological pH (7.4). Finally, the IC ₅₀ of this ELA‐GO nanocomposite was found to be 6.16 µg/ml against B16 cell line; ELA and GO did not show any cytotoxic effects up to 50 µg/ml on the same cell lines.     

Polar and longitudinal magneto-optical spectroscopy of bismuth substituted yttrium iron garnet films grown by pulsed laser deposition

Ferrimagnetic bismuth substituted yttrium iron garnet Bi_xY_3 − xFe₅O₁₂ (BiYIG) films with x = 1 and 2 pulsed laser deposited onto (111) Gd₃Ga₅O₁₂ (GGG) substrates were studied using magneto-optical (MO) Kerr spectroscopy in the photon energy range of 1.8-5 eV at both polar and longitudinal magnetizations. The interference at lower photon energies provided the refined film thicknesses ranging between 70 and 200 nm. The films were grown under compressive strain and displayed saturation magnetizations (μ₀M_s) lower than that of their bulk counterparts due to the presence of nanograins forming BiYIG layers and/or magnetically dead interface layers. The trends in the MO spectra agree with those deduced from the published permittivity tensor data for BiYIG using a transfer matrix model applied to a film (BiYIG)-substrate (GGG) system. Due to the reduced μ₀M_s the predicted amplitudes are typically higher. The agreement was improved using effective medium approach or by incorporating into the model MO passive interface layers. The information on MO activity at longitudinal magnetization in the garnet layers below 100 nm presents interest for MO imaging and magnetophotonic devices. The results suggest that the MO Kerr spectroscopy combined with MO Kerr magnetometry may represent a valuable, cheap and nondestructive tool for the characterization of magnetic garnet films less than 200 nm thick.     

Powder X-Ray Reference Patterns of Sr2RGaCu2Oy (R = Pr,Nd, Sm,Eu, Gd,Dy, Ho,Er, Tm,and Y)

X-Ray Rietveld refinements were conducted on a series of eleven lanthanide phases, Sr₂RGaCu₂O_y (2112 phase, R = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm, and Yb) that are structurally related to the high T_c superconductor Ba₂YCu₃O₇ (213). In the 2112 structure, instead of square planar Cu-O chains, tetrahedral GaO4 chains were found to run in a zig-zag fashion along the diagonal of the basal 213 ab-direction. Reference powder patterns for these compounds were prepared by using the Rietveld decomposition technique. The unit cell volume of these compounds follows the expected trend of the lanthanide contraction. The lattice parameters range from a = 22.9694(3) Å, b = 5.5587(2) Å, and c = 5.44743(7) Å for R = Pr, to a = 22.8059(2) Å, b = 5.46031(5) Å, and c = 5.37773(5) Å for R = Yb. An electon diffraction study of the Sm- and Er-analogs showed characteristic diffuse streaks along the b-axis, suggesting some disorder within the GaO₄ chains.     

Zirconium and hafnium oxide interface with silicon: Computational study of stress and strain effects

Computations of the periodic double-interface MO₂/Si (M = Zr and Hf) systems using density functional theory (DFT) demonstrate that very thin epitaxial MO₂ layers at silicon (1 0 0) surface adopt anatase-like structure with six-coordinate M atoms, while tetragonal-like MO₂ structure with seven-coordinated M atoms has a lower stability (metastable). This results from a closer match between Si(1 0 0) surface unit cell and anatase-like ZrO₂ and HfO₂ leading to the overall stress reduction if MO₂ adopts the anatase-like structure on silicon. In agreement with the previous study of Gavartin et al. [Gavartin, Fonseca, Bersuker, Shluger, Microelectron. Eng. 80 (2005) 412–415] formation of oxygen vacancy at the interface is demonstrated to be lower than in bulk film. This result appears to be independent from the film or interface structure but originates from the energy balance between M–O, M–M, Si–O and M–Si bonds, as revealed by a simple molecular model.     

Tables of the Inverse Laplace Transform of the Function [... formula ...]

The inverse transform, g(t) = ?^?1(e^?sβ), 0 < β < 1, is a stable law that arises in a number of different applications in chemical physics, polymer physics, solid-state physics, and applied mathematics. Because of its important applications, a number of investigators have suggested approximations to g(t). However, there have so far been no accurately calculated values available for checking or other purposes. We present here tables, accurate to six figures, of g(t) for a number of values of β between 0.25 and 0.999. In addition, since g(t), regarded as a function of β, is uni-modal with a peak occurring at t = t_max we both tabulate and graph t_max and 1/g(t_max) as a function of β, as well as giving polynomial approximations to 1/g(t_max).     

Atomic force microscopy of the morphology and mechanical behaviour of barnacle cyprid footprint proteins at the nanoscale

Barnacles are a major biofouler of man-made underwater structures. Prior to settlement, cypris larvae explore surfaces by reversible attachment effected by a ‘temporary adhesive’. During this exploratory behaviour, cyprids deposit proteinaceous ‘footprints’ of a putatively adhesive material. In this study, footprints deposited by Balanus amphitrite cyprids were probed by atomic force microscopy (AFM) in artificial sea water (ASW) on silane-modified glass surfaces. AFM images obtained in air yielded better resolution than in ASW and revealed the fibrillar nature of the secretion, suggesting that the deposits were composed of single proteinaceous nanofibrils, or bundles of fibrils. The force curves generated in pull-off force experiments in sea water consisted of regions of gradually increasing force, separated by sharp drops in extension force manifesting a characteristic saw-tooth appearance. Following the relaxation of fibrils stretched to high strains, force–distance curves in reverse stretching experiments could be described by the entropic elasticity model of a polymer chain. When subjected to relaxation exceeding 500 ms, extended footprint proteins refolded, and again showed saw-tooth unfolding peaks in subsequent force cycles. Observed rupture and hysteresis behaviour were explained by the ‘sacrificial bond’ model. Longer durations of relaxation (>5 s) allowed more sacrificial bond reformation and contributed to enhanced energy dissipation (higher toughness). The persistence length for the protein chains (L_P) was obtained. At high elongation, following repeated stretching up to increasing upper strain limits, footprint proteins detached at total stretched length of 10 µm.     

A combinatorial characterization scheme for high-throughput investigations of hydrogen storage materials

In order to increase measurement throughput, a characterization scheme has been developed that accurately measures the hydrogen storage properties of materials in quantities ranging from 10 ng to 1 g. Initial identification of promising materials is realized by rapidly screening thin-film composition spread and thickness wedge samples using normalized IR emissivity imaging. The hydrogen storage properties of promising samples are confirmed through measurements on single-composition films with high-sensitivity (resolution <0.3 μg) Sievert’s-type apparatus. For selected samples, larger quantities of up to ∼100 mg may be prepared and their (de)hydrogenation and micro-structural properties probed via parallel in situ Raman spectroscopy. Final confirmation of the hydrogen storage properties is obtained on ∼1 g powder samples using a combined Raman spectroscopy/Sievert’s apparatus.     

Molecular dynamics study of dipalmitoylphosphatidylcholine lipid layer self-assembly onto a single-walled carbon nanotube

Single-walled carbon nanotubes (SWNTs) are possible nano-injectors and delivery vehicles of molecular probes and drugs into cells. In order to explore the interaction between lipid membranes and carbon nanotubes, we investigate the binding mechanism of dipalmitoylphosphatidylcholine (DPPC) with SWNTs by molecular dynamics. In low concentration range simulations, the DPPC molecules form a supramolecular two-layered cylindrical structure wrapped around the carbon nanotube surface. The hydrophobic part of DPPC is adsorbed on the surface of the nanotube, and the hydrophilic top is oriented towards the aqueous phase. For higher concentration ranges, the DPPC molecules are found to form a supramolecular multi-layered structure wrapped around the carbon nanotube surface. At the saturation point a membrane-like structure is self-assembled with a width of 41.4 Å, which is slightly larger than the width of a cell membrane. Our study sheds light on the existing conflicting simulation data on adsorption of single-chained phospholipids.      

Adsorption of amino acids by fullerenes and fullerene nanowhiskers

We have investigated the adsorption of some amino acids and an oligopeptide by fullerene (C₆₀) and fullerene nanowhiskers (FNWs). C₆₀ and FNWs hardly adsorbed amino acids. Most of the amino acids used have a hydrophobic side chain. Ala and Val, with an alkyl chain, were not adsorbed by the C₆₀ or FNWs. Trp, Phe and Pro, with a cyclic structure, were not adsorbed by them either. The aromatic group of C₆₀ did not interact with the side chain. The carboxyl or amino group, with the frame structure of an amino acid, has a positive or negative charge in solution. It is likely that the C₆₀ and FNWs would not prefer the charged carboxyl or amino group. Tri-Ala was adsorbed slightly by the C₆₀ and FNWs. The carboxyl or amino group is not close to the center of the methyl group of Tri-Ala. One of the methyl groups in Tri-Ala would interact with the aromatic structure of the C₆₀ and FNWs. We compared our results with the theoretical interaction of 20 bio-amino acids with C₆₀. The theoretical simulations showed the bonding distance between C₆₀ and an amino acid and the dissociation energy. The dissociation energy was shown to increase in the order, Val < Phe < Pro < Asp < Ala < Trp < Tyr < Arg < Leu. However, the simulation was not consistent with our experimental results. The adsorption of albumin (a protein) by C₆₀ showed the effect on the side chains of Try and Trp. The structure of albumin was changed a little by C₆₀. In our study Try and Tyr were hardly adsorbed by C₆₀ and FNWs. These amino acids did not show a different adsorption behavior compared with other amino acids. The adsorptive behavior of mono-amino acids might be different from that of polypeptides.     

Interlaboratory Comparison of Magnetic Thin Film Measurements

A potential low magnetic moment standard reference material (SRM) was studied in an interlaboratory comparison. The mean and the standard deviation of the saturation moment m_s, the remanent moment m_r, and the intrinsic coercivity H_c of nine samples were extracted from hysteresis-loop measurements. Samples were measured by thirteen laboratories using inductive-field loopers, vibrating-sample magnetometers, alternating-gradient force magnetometers, and superconducting quantum-interference-device magnetometers. NiFe films on Si substrates had saturation moment measurements reproduced within 5 % variation among the laboratories. The results show that a good candidate for an SRM must have a highly square hysteresis loop (m_r/m_s > 90 %), H_c ≈ 400 A·m⁻¹ (5 Oe), and m_s ≈ 2 × 10⁻⁷ A·m² (2 × 10⁻⁴ emu).     

Micro/nanoscale mechanical characterization and in situ observation of cracking of laminated Si3N4/BN composites

Micro/nanoscale mechanical characterization of laminated Si₃N₄/BN composites was carried out by nanoindentation techniques. A custom-designed micro mechanical tester was integrated with an optical microscope and an atomic force microscope to perform in situ three-point bending tests on notched Si₃N₄/BN composite bend specimens where the crack initiation and propagation were imaged simultaneously with the optical microscope and atomic force microscope during bending loading. The whole fracture process was in situ captured. It was found that crack deflection was initiated/induced by the pre-existing microvoids and microcracks in BN interfacial layers. New fracture mechanisms were proposed to provide guidelines for the design of biomimetic nacre-like composites.     

Invasion,persistence and control in epidemic models for plant pathogens: the effect of host demography

Many epidemiological models for plant disease include host demography to describe changes in the availability of susceptible tissue for infection. We compare the effects of using two commonly used formulations for host growth, one linear and the other nonlinear, upon the outcomes for invasion, persistence and control of pathogens in a widely used, generic model for botanical epidemics. The criterion for invasion, reflected in the basic reproductive number, R₀, is unaffected by host demography: R₀ is simply a function of epidemiological parameters alone. When, however, host growth is intrinsically nonlinear, unexpected results arise for persistence and the control of disease. The endemic level of infection (I_∞) also depends upon R₀. We show, however, that the sensitivity of I_∞ to changes in R₀ > 1 depends upon which underlying epidemiological parameter is changed. Increasing R₀ by shortening the infectious period results in a monotonic increase in I_∞. If, however, an increase in R₀ is driven by increases in transmission rates or by decreases in the decay of free-living inoculum, I_∞ first increases (R₀ < 2), but then decreases (R₀ > 2). This counterintuitive result means that increasing the intensity of control can result in more endemic infection.     

Liquidus Diagram of the Ba-Y-Cu-O System in the Vicinity of the Ba2YCu3O6+x Phase Field

This paper describes the melting equilibria in the vicinity of the high T_c phase Ba₂YCu₃O_6+x, including evidence for two Ba-Y-Cu-O immiscible liquids. Melting equilibria have been investigated in purified air using a combination of differential thermal analysis (DTA), thermogravimetric analysis (TGA), powder x-ray diffraction (XRD), MgO wick entrapment of liquid for analysis, scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDS), and hydrogen reduction for determination of copper oxidation state. For relatively barium-rich compositions, it was necessary to prepare the starting materials under controlled atmosphere conditions using BaO. A liquidus diagram was derived from quantitative data for the melts involved in various melting reactions. In general the 1/2(Y₂O₃) contents of the melts participating in these equilibria were low (mole fraction <4 %). The primary phase field of Ba₂YCu₃O_6+x occurs at a mole fraction of <2.0 % 1/2Y₂O₃ and lies very close along the BaO-CuO_x edge, extending from a mole fraction of ≈43 % CuO to a mole fraction of ≈76 % CuO. It is divided by a liquid miscibility gap and extends on either side about this gap. The topological sequence of melting reactions associated with the liquidus is presented as a function of temperature. Implications for the growth of Ba₂YCu₃O_6+x crystals are discussed.