Direct printing of self-assembled lipid tubules on substrates

Lipid tubules formed by rolled-up bilayer sheets have shown promise in drug delivery systems, nanofluidics, and microelectronics. Here we report a method for directly printing lipid tubules on substrates. Preformed lipid tubules of 1,2-bis(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine are aligned in the recessed channels of a thin poly(dimethylsiloxane) (PDMS) stamp. The aligned lipid tubules then serve as an "ink" for microcontact printing. We demonstrate that two-dimensional (2-D) arrays of aligned lipid tubules can be transferred onto planar, patterned, and curved substrates from the recessed channels of the PDMS stamp by bringing the tubule-inked PDMS stamp into contact with these substrates. We show that the 2-D array of aligned lipid tubules can be transcribed into a 2-D array of aligned silica cylinders through templated sol-gel condensation of tetraethoxysilane.     

Zigzag lipid tubules

We report a method based on poly(dimethylsiloxane) (PDMS) stamp-assisted moving contact line to bend lipid tubules into zigzags on glass substrates. Atomic force microscopy (AFM) reveals that the zigzag lipid tubules buckle at the bent sites. The measurements of buckling heights as a function of bending angles suggest a gradual buckling mode. By imaging the zigzag tubules with AFM under different loading forces, we study the correlation between the loading force and the tubule compression. The reduced stiffness at the buckling sites of zigzag tubules suggests that lipid molecules are reorganized during the gradual buckling.     

Bending and radial deformation of lipid tubules on self-assembled thiol monolayers

Lipid tubules represent a hollow, cylindrical supramolecular structure formed by rolled-up lipid bilayers. We find that the lipid tubules of 1,2-bis(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine can be bent into a loopike shape by the shrinking contact line of droplets on self-assembled monolayers (SAMs) of 1-dodecanethiol. The persistence length of individual lipid tubules is estimated to be approximately 41 microm. The radial deformation of the lipid tubules on SAMs is studied under applied load using atomic force microscope. The stiffness of the tubules in the radial direction is found to increase when the number of the lipid bilayers in the tubule wall increases.     

Patterning polymerized lipid vesicles with soft lithography

The applications of soft lithography in patterning polymerized lipid vesicles of 1,2-bis(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine on glass substrates are reported. We demonstrate that the polymerized vesicles can be used as a high molecular weight ink to be transferred from a PDMS stamp onto a glass substrate to form two-dimensional stripes with a controlled separation. By combining channel flow with dewetting within microfluidic networks, we assemble the polymerized vesicle into three-dimensional stripes and one-dimension lines on glass substrates. Atomic force microscopy shows that these patterned vesicle structures are stable on glass substrates. The simple, stable, and precise immobilization of lipid vesicles on solid substrates will open up the possibility of integrating them in biosensors and microelectronic devices.     

Positioning and alignment of lipid tubules on patterned Au substrates

This paper presents a method for positioning and aligning self-assembled tubules of 1,2-bis(tricosa-10,12-diynoyl)-sn-glycero-3-phosphochloline (DC(8,9)PC) by withdrawing a patterned Au substrate from tubule solution. The patterned Au substrates with alternating bare Au stripes and thiol monolayer stripes are formed by microcontact printing. We find that the lipid tubules selectively adsorb on the bare Au stripes but show no orientation order. By withdrawing the patterned Au substrates at the direction along the stripes from tubule solution, the lipid tubules are found to be aligned along the direction of the Au stripes. The angular distribution and the density of the aligned lipid tubules depend on the withdrawal rates and the adsorption time, respectively. We conclude that forces causing tubule alignment that originate in the surface tension associated with the moving meniscus dominate alignment forces exerted by the patterned Au substrates.     

Subnanometer actuation of a tethered lipid bilayer monitored with fluorescence resonance energy transfer

Lipid membrane nanotechnology can play a key role in preserving the function of transmembrane proteins on biofunctional substrates. We show here that rational nanoscopic actuation of a polymer-tethered lipid bilayer can be achieved by modulating the dielectric environment at the membrane-substrate interface. This provides a hydrated platform with increased lipid mobility compared to bilayers supported directly onto silica. We suggest that this construct may be used for promoting the functional reconstitution of transmembrane proteins on planar surfaces for bioanalytical devices.     

Self-assembly of poly(N-isopropylacrylamide)-carrying microspheres into two-dimensional colloidal arrays

Droplets containing polymer particles were deposited on a substrate. Poly(N-isopropylacrylamide) (PNIPAM) hydrogel and particles with PNIPAM graft chains on the surface self-assembled into a two-dimensional (2-D) superlattice when their dilute dispersions were dried on substrates. The capillary force between the particles induced ordered array formation during water evaporation. The presence of a PNIPAM layer on the particle surface gave the particles steric stability during ordered array formation. By grafting PNIPAM chains on particle surfaces by living radical polymerization, we successfully controlled the structural patterns of the colloidal arrays. These, controllable, 2-D colloidal arrays were generated on various substrates upon air-drying.     

Lipid nanotubule fabrication by microfluidic tweezing

There is currently great interest in the development of lipid enclosed systems with complex geometrical arrangements that mimic cellular compartments. With biochemical functionalization, these soft matter devices can be used to probe deeper into life's transport dominated biochemical operations. In this paper, we present a novel tool for machining lipid nanotubules by microfluidic tweezing. A bilayer poly(dimethylsiloxane) (PDMS) device was designed with a lipid reservoir that was loaded by capillary action for lipid film deposition. The lipid reservoir is vertically separated from an upper flow for controlled material wetting and the formation of giant tubule bodies. Three fluidic paths are interfaced for introduction of the giant tubules into the high velocity center of a parabolic flow profile for exposure to hydrodynamic shear stresses. At local velocities approximating 2 mm s (-1), a 300-500 nm diameter jet of lipid material was tweezed from the giant tubule body and elongated with the flow. The high velocity flow provides uniform drag for the rapid and continuous fabrication of lipid nanotubules with tremendous axial ratios. Below a critical velocity, a remarkable shape transformation occurred and the projected lipid tubule grew until a constant 3.6 mum diameter tubule was attained. These lipid tubules could be wired for the construction of advanced lifelike bioreactor systems.     

Nanoscale wettability of self-assembled monolayers investigated by noncontact atomic force microscopy

We report on a novel technique to nucleate nanometer-sized droplets on a solid substrate and to image them with minimal perturbation by noncontact atomic force microscopy (NC-AFM). The drop size can be accurately controlled, thus permitting hysteresis measurements. We have studied the nanoscale wettability of several methyl-terminated substrates prepared by the self-assembly of organic molecules. These substrates are alkyltrichlorosilanes on silica, alkylthiols on gold, alkyl chains on hydrogen-terminated silicon, and crystalline hexatriacontane chains on silica. For each of these systems, we report a deviation of the wetting contact angle from the macroscopic value, and we discuss this effect in term of mesoscale surface heterogeneity and long-range solid-liquid interactions.     

Characterization of the physical properties of model biomembranes at the nanometer scale with the atomic force microscope

Interaction forces and topography of mixed phospholipid-glycolipid bilayers were investigated by atomic force microscopy (AFM) in aqueous conditions with probes functionalized with self-assembled monolayers terminating in hydroxy groups. Short-range repulsive forces were measured between the hydroxy-terminated probe and the surface of the two-dimensional (2-D) solid-like domains of distearoyl-phosphatidylethanolamine (DSPE) and digalactosyldiglyceride (DGDG). The form and range of the short-range repulsive force indicated that repulsive hydration/steric forces dominate the interaction at separation distances of 0.3-1.0 nm after which the probe makes mechanical contact with the bilayers. At loads < 5 nN the bilayer was elastically deformed by the probe, while at higher loads plastic deformation of the bilayer was observed. Surprisingly, a short-range repulsive force was not observed at the surface of the 2-D liquid-like dioleoylphosphatidylethanolamine (DOPE) film, despite the identical head groups of DOPE and DSPE. This provides direct evidence for the influence of the structure and mechanical properties of lipid bilayers on their interaction forces, an effect which may be a major importance in the control of biological processes such as cell adhesion and membrane fusion. The step height measured between lipid domains in the AFM topographic images was larger than could be accounted for by the thickness and mechanical properties of the molecules. A direct correlation was observed between the repulsive force range over the lipid domains and the topographic contrast, which provides direct insight into the fundamental mechanisms of AFM imaging in aqueous solutions. This study demonstrates that chemically modified AFM probes can be used in combination with patterned lipid bilayers as a novel and powerful approach to characterize the nanometer scale chemical and physical properties of heterogeneous biosurfaces such as cell membranes.     

Probing colloidal forces between a Si3N4 AFM tip and single nanoparticles of silica and alumina

The atomic force microscope (AFM) has been used to measure surface forces between silicon nitride AFM tips and individual nanoparticles deposited on substrates in 10(-4) and 10(-2) M KCl solutions. Silica nanoparticles (10 nm diameter) were deposited on an alumina substrate and alumina particles (5 to 80 nm diameter) were deposited on a mica substrate using aqueous suspensions. Ionic concentrations and pH were used to manage attractive substrate-particle electrostatic forces. The AFM tip was located on deposited nanoparticles using an operator controlled offset to achieve stepwise tip movements. Nanoparticles were found to have a negligible effect on long-range tip-substrate interactions, however, the forces between the tip and nanoparticle were detectable at small separations. Exponentially increasing short-range repulsive forces, attributed to the hydration forces, were observed for silica nanoparticles. The effective range of hydration forces was found to be 2-3 nm with the decay length of 0.8-1.3 nm. These parameters are in a good agreement with the results reported for macroscopic surfaces of silica obtained using the surface force apparatus suggesting that hydration forces for the silica nanoparticles are similar to those for flat silica surfaces. Hydration forces were not observed for either alumina substrates or alumina nanoparticles in both 10(-4) M KCl solution at pH 6.5 and 10(-2) M KCl at pH 10.2. Instead, strong attractive forces between the silicon nitride tip and the alumina (nanoparticles and substrate) were observed.     

Patterning of sol gel thin films by capillary force assisted soft lithographic technique

Patterning of sol gel based silica and silica–titania films has been developed at room temperature by soft lithographic technique. Corresponding metal alkoxides have been utilized for the preparation of precursor sols. Elastomeric stamps of polydimethylsiloxane (PDMS) are used to emboss patterns of a master grating on the as-prepared silica and silica–titania films obtained by sol gel process. Pressure-less capillary force lithography has been used to fabricate both 1-D and 2-D ordered structures of simple stripe patterns. A modified solvent assisted lithography and micro-molding in capillaries yielded stable and high fidelity 1-D structures for silica and silica–titania films over a large area.     

Deposition features of Ni on self-assembled microtubule template from biolipid by electroless method

The self-assembly of lipid molecules is in close relationship with the structure and function of a cell membrane. A cell membrane has a variety of lipid molecules. Lipid molecules have their amphiphile na-tures, and their self-assembly can form a variety of thermodynamically stable microstructures, such as single-bilayer or multi-bilayer spherical and ellipsoidal liposome, microcylindrical and microtubular struc-tures[1]. These microstructures exhibit different bio-logical functions in living …     

A preliminary study on chemical micro-machining of complex three-dimensional patterns on silicon substrates

Chemical micro-machining of complex 3-dimensional (3-D) patterns of silicon substrates was preliminarily explored by the confined etchant layer technique (CELT). Through systematic investigation, we demonstrated that cysteine as a scavenger and Br₂ as an etchant can be used to etch silicon substrates. The CELT has the potential to develop into a new means of micro-machining complex 3-D patterns on silicon substrates. However, due to the highly corrosive property of the chemicals used for the silicon etched system, great effort must be made to overcome these problems including the mold electrode with high chemical stability.Dedicated to Professor Gygy Horyi on the occasion of his 70th birthday     

Structure of anionic phospholipid coatings on silica by dissipative quartz crystal microbalance

The adsorption of anionic phospholipids on silica was investigated by the dissipative quartz crystal microbalance (QCM) technique. Liposomes composed of 1 mM 80:20 mol % of 1-palmitoyl-2-oleyl-sn-glycero-3-phosphatidylcholine (POPC)/phosphatidic acid, POPC/phosphatidylglycerol, or POPC/phosphatidylserine in N-(2-hydroxyethyl)piperazine-N'-(2-ethanesulfonic acid) buffer at pH 7.4 (with or without 3 mM of CaCl2) were examined. We have previously demonstrated that similar phospholipid coatings can be used in capillary electrochromatography as a stationary phase for the separation of analytes. In this work, we focus on the formation of the coatings and on the type of lipid structure formed on silica. The QCM investigation comprised qualitative results based on changes in frequency and resistance, and quantitative modeling of the obtained results. The latter was performed using the dissipative QCM, which measures the quartz crystal impedance, combined with equivalent circuit analysis. A previously developed coating and cleaning procedure for phospholipid-coated fused silica capillaries was adopted in this study, and the same silica-coated crystal was used throughout the QCM study. We will demonstrate in this work that the type of lipid structure formed on silica, that is, a rather rigid supported lipid bilayer or a viscoelastic supported vesicle layer (SVL), is highly dependent on the lipid and solvent composition. We also show for the first time that the modeling of the dissipative QCM data can be used to extract a more quantitative picture of an adsorbed SVL, because, so far, published studies have merely used the QCM data in a qualitative sense.     

高分散性SiO_2/PMMA复合材料的制备与表征——稀释分散性

以高无机含量SiO2/聚甲基丙烯酸甲酯(PMMA)接枝复合材料为预分散母料,与PMMA树脂进行熔融共混,制得低无机含量的SiO2/PMMA复合材料.通过切片透射电镜(TEM)观察熔融共混过程中预分散母料内堆积SiO2粒子分散状态的演化.发现预分散母料接枝状态对其影响最为显著,不经接枝修饰的SiO2粒子经熔融共混后,不可避免地会在熔体中产生大量亚微米级的立体团聚体;复杂接枝预分散母料内构成以SiO2粒子为交联点的立体交联结构,其中的堆积SiO2粒子不能在剪切场中得到有效解离和释放;只有在使用简单接枝预分散母料时,基体高分子链才能不断地渗透扩散进入预分散母料内,而预分散母料可被不断地溶胀和撕裂,因而其中的堆积SiO2才可不断地向基体相迁移和扩散,并最终在整个复合材料内实现初级粒子形式的高度均匀稳定分散.     

Palladium Nanotubes Formed by Lipid Tubule Templating and Their Application in Ethanol Electrocatalysis

Palladium nanotubes were fabricated by using lipid tubules as templates for the first time in a controlled manner. The positively charged lipid 1,2‐dioleoyl‐3‐trimethylammoniumpropane (DOTAP) was doped into lipid tubules to adsorb PdCl₄^2? on the tubule surfaces for further reduction. The lipid tubule formation was optimized by studying the growing dynamics and ethanol/water ratio. The DOTAP‐doped tubules showed pH stability from 0 to 14, which makes them ideal templates for metal plating. The Pd nanotubes are open‐ended with a tunable wall thickness. They exhibited good electrocatalytic performance in ethanol. Their electrochemically active surface areas were 6.5, 10.6, and 83.2 m² g^?1 for Pd nanotubes with 77, 101, and 150 nm wall thickness, respectively. These Pd nanotubes have great potential in fuel cells. The method demonstrated also opens up a way to synthesize hollow metal nanotubes.     

Langmuir-Blodgett films of fluorinated glycolipids and polymerizable lipids and their phase separating behavior

This paper describes the phase separating behavior of Langmuir monolayers from mixtures of different lipids that (i) either carry already a glycopeptide recognition site or can be easily modified to carry one and (ii) polymerizable lipids. To ensure demixing during compression, we used fluorinated lipids for the biological headgroups and hydrocarbon based lipids as polymerizable lipids. As a representative for a lipid monomer, which can be polymerized in the hydrophilic headgroup, a methacrylic monomer was used. As a monomer, which can be polymerized in the hydrophobic tail, a lipid with a diacetylene unit was used (pentacosadiynoic acid, PDA). The fluorinated lipids were on the one hand a perfluorinated lipid with three chains and on the other hand a partially fluorinated lipid with a T(N)-antigen headgroup. The macroscopic phase separation was observed by Brewster angle microscopy, whereas the phase separation on the nanoscale level was observed by atomic force microscopy. It turned out that all lipid mixtures showed (at least) a partial miscibility of the hydrocarbon compounds in the fluorinated compounds. This is positive for pattern formation, as it allows the formation of small demixed 2D patterned structures during crystallization from the homogeneous phase. For miscibility especially a liquid analogue phase proved to be advantageous. As lipid 3 with three fluorinated lipid chains (very stable monolayer) is miscible with the polymerizable lipids 1 and 2, it was mostly used for further investigations. For all three lipid mixtures, a phase separation on both the micrometer and the nanometer level was observed. The size of the crystalline domains could be controlled not only by varying the surface pressure but also by varying the molar composition of the mixtures. Furthermore, we showed that the binary mixture can be stabilized via UV polymerization. After polymerization and subsequent expansion of the barriers, the locked-in polymerized structures are stable even at low surface pressures (10 mN/m), where the unpolymerized mixture did not show any segregation.     

Stability of lipid films formed on gamma-aminopropyl monolayers

The stability of supported lipid membranes (SLMs) deposited on planar substrates derivatized with (gamma-aminopropyl)silane (GAPS) was examined. Ellipsometry, fluorescence microscopy, and atomic force microscopy were used to characterize SLMs exposed to repeated drying and rehydration. Vesicle fusion on GAPS-coated substrates produced SLMs with a thickness significantly greater than that of a single lipid bilayer. Exposure to even one cycle of drying/rehydration significantly decreased the thickness of a SLM on GAPS, and repeated drying/rehydration resulted in near quantitative lipid desorption. Thus SLMs on GAPS do not appear to be significantly more stable than the single bilayer SLM that is formed on bare glass or SiO2 under equivalent conditions.     

Surface chemistry and rheology of polysulfobetaine-coated silica

We have measured the viscosity of suspensions of colloidal silica particles (d = 300 nm) and the properties of silica surfaces in solutions of a polymer consisting of zwitterionic monomer groups, poly(sulfobetaine methacrylate), polySBMA. This polymer has potential use in modifying surface properties because the polymer is net uncharged and therefore does not generate double-layer forces. The solubility of the polymer can be controlled and varies from poor to good by the addition of sodium chloride salt. Ellipsometry was used to demonstrate that polySBMA adsorbs to silica and exhibits an increase in surface excess at lower salt concentration, which is consistent with a smaller area per molecule at low salt concentration. Neutron reflectivity measurements show that the adsorbed polymer has a thickness of about 3.7 nm and is highly hydrated. The polymer can be used to exercise considerable control over suspension rheology. When silica particles are not completely covered in polymer, the suspension produces a highly viscous gel. Atomic force microscopy was used to show this is caused by bridging of polymer between the particles. At higher surface coverage, the polymer can produce either a high or very low viscosity slurry depending on the sodium chloride concentration. At high salt concentration, the suspension is stable, and the viscosity is lower. This is probably because the entrainment of many small ions renders the polymer film highly hydrophilic, producing repulsive surface forces and lubricating the flow of particles. At low salt concentrations, the polymer is barely soluble and more densely adsorbed. This produces less stable and more viscous solutions, which we attribute to attractive interactions between the adsorbed polymer layers.