Temperature-dependent formation of octadecylsiloxane self-assembled monolayers on mica as studied by atomic force microscopy

We have investigated the growth of octadecylsiloxane (ODS) self-assembled monolayers on mica. Freshly cleaved muscovite mica and octadecyltrichlorosilane (OTS) dissolved in toluene (c = 1.0 mmol/L) have been used as substrate and precursor, respectively. The water content of the adsorption solution was between 14.6 and 16.6 mmol/L. Adsorption experiments were carried out in a temperature range between 5 and 45 degrees C, and the obtained submonolayer ODS films were characterized with atomic force microscopy (AFM). Besides the morphology of the films, also information on the surface coverage has been obtained by quantitative evaluation of the AFM images. Depending on the temperature, evidence for both ordered and disordered expanded ODS phases has been found. The pronounced maximum in surface coverage--in contrast to adsorption on silicon substrates--at a temperature of about 27 degrees C and the different morphology of the submonolayer films as compared to silicon substrates could be explained in terms of a deposition, diffusion, and aggregation (DDA) model.     

Nanoscale patterning of alkyl monolayers on silicon using the atomic force microscope

Self-assembled monolayers (SAMs) of 1-alkenes on hydrogen-passivated silicon substrates were successfully patterned on the nanometer scale using an atomic force microscope (AFM) probe tip. Nanoshaving experiments on alkyl monolayers formed on H-Si(111) not only demonstrate the flexibility of this technique but also show that patterning with an AFM probe is a viable method for creating well-defined, nanoscale features in a monolayer matrix in a reproducible and controlled manner. Features of varying depths (2-15 nm) were created in the alkyl monolayers by controlling the applied load and the number of etching scans made at high applied loads. The patterning on these SAM films is compared with the patterning of alkyl siloxane monolayers on silicon and mica.     

An atomic force microscopy study of asphaltenes on mica surfaces. Influence of added resins and demulsifiers

 Monolayers of asphaltene and resins on the water surface have been transferred at a surface pressure of 10 mN/m onto mica substrates using the Langmuir–Blodgett technique. Atomic force microscopy (AFM) has been used to examine the topography of these layers. Monolayers consisting of pure asphaltene fractions provide a rigid film with a close-packed structure, while the resins build up a continuous open network. Mixed films of these two fractions show that a gradual increase in resin concentration leads to an opening of the rigid asphaltene structure towards a more resin like configuration. Increased aggregation when the two heavy functions are present in one film is seen as larger individual units in the AFM pictures. Addition of high-molecular-weight demulsifiers/inhibitors results in the same kind of influence on the asphaltene film as seen with the resins. Received: 30 April 1999 Accepted: 29 November 1999     

Direct observation of surfactant aggregate behavior on a mica surface using high-speed atomic force microscopy

The processes of dynamic aggregate transformations of micelles at a mica surface were observed using high-speed atomic force microscopy. We showed that salt concentration affects not only the equilibrium state adsorbed structure but also the time required to reach the equilibrium state on the mica surface.     

Generic phase behavior of branched-chain phospholipid monolayers

Monolayers of chemically modified triple-chain phospholipids have been investigated at the air/water interface using pressure-area isotherms. The condensed phases of the lipids were characterized by grazing incidence X-ray diffraction (GIXD). Increasing chain length corresponds to a temperature effect, which was quantified for different lipids, depending on the head group structure using isotherm (two-dimensional systems) and DSC (three-dimensional systems) measurements. The combination of structure investigations revealed generic phase diagrams, which describe the phase behavior of multiple-chain lipids in two dimensions. For the 1-acyl-2-O-alkyl phospholipids, the generic phase diagram exhibits only L(2d), LS and LE phases while the exchange of the position of the branched acyl and the non-branched alkyl chains at the glycerol backbone leads to a much richer polymorphism (L(2h), L(2d), Ov, LS, S, tau, LE). Here we present the first experimental evidence of the unusual tau phase for multiple-chain lipid monolayers. This phase exhibits an undistorted in-plane lattice despite of tilted chains.     

Oligo(ethylene glycol)-terminated monolayers on silicon surfaces and their nanopatterning with a conductive atomic force microscope

Functionalization of silicon substrate surfaces with a stable monolayer for resisting non-specific adsorption of proteins has attracted great interest,since it is directly relevant to the development of miniature,silicon-based biosensors and implantable microdevices,such as silicon-neuron interfaces.This brief review summarizes our contribution to the development of robust monolayers grown by surface hydrosilylation on atomically flat,hydrogen-terminated silicon surfaces.The review also outlines our strateg...     

Liquid mechanical behavior of mixed monolayers of amino and alkyl silanes by atomic force microscopy

The adsorption of mixed terminally aminated organosilyl compounds with long-chain n-alkyltrichlorosilanes on silica substrates has been studied by FTIR and AFM to deposit and study DNA. By optimization of deposition conditions, the mixed monolayers were found to be well organized and homogeneous. The amino group was protected to obtain a reproducible grafting and then deprotected after the film formation. In addition, atomic force microscopy (AFM) studies in both dynamical modes, amplitude modulation and frequency modulation, reveal that the layer behaves as a fluid as measured by the tip-cantilever and has a smaller characteristic time than the tip-cantilever. For three amplitudes, the experimental frequency shifts have been modeled for a fluidlike layer crossed by the tip. Finally, we show that this new fluidlike monolayer is suitable for DNA deposition and AFM studies.     

Properties of oxidized phospholipid monolayers: An atomistic molecular dynamics study

Non-saturated lipids in the lung surfactant are prone to oxidation by oxidative species present in air. In this Letter, oxidized monolayers of dioleoylphosphatidylcholine (DOPC) were studied by means of both molecular dynamics and potential of mean force calculations. Structural changes of the monolayer following oxidation were revealed, including orientational reversal of oxidized chains. Accumulation of oxidized lipids in the monolayer is observed for moderate oxidation ratios, whereas removal of the short-chain oxidation product is predicted at long timescales. Massive oxidation leads to the loss of the well-ordered monolayer structure and partial solubilization of the oxidized lipids in the aqueous subphase.     

Adsorption behavior of hexadecyltrimethylammonium bromide (CTAB) to mica substrates as observed by atomic force microscopy

The study of the adsorption behavior of surfac-which makes people further study the adsorptiontants to interfaces is very important in colloid and in-mechanism at the molecular level.terface science[1]owing to the important applications In situ AFM measur…     

Probing small unilamellar EggPC vesicles on mica surface by atomic force microscopy

Sonicated small unilamellar egg yolk phosphatidylcholine (EggPC) vesicles were investigated using atomic force microscopy (AFM) imaging and force measurements. Three different topographies (convex, planar, and concave shape) of the EggPC vesicles on the mica surface were observed by tapping mode in fluid, respectively. It was found that the topography change of the vesicles could be attributed to the interaction force between the AFM tip and vesicles. Force curves between an AFM tip and an unruptured vesicle were obtained in contact mode. During approach, two breaks corresponding to the abrupt penetration of upper and lower bilayer of vesicle were exhibited in the force curve. Both breaks spanned a distance of around 4 nm close to the EggPC bilayer thickness. Based on Hertz analysis of AFM approach force curves, the Young's modulus (E) and the bending modulus (kc) for pure EggPC vesicles were measured to be (1.97 +/- 0.75) x 10(6)Pa and (0.21 +/- 0.08) x 10(-19)J, respectively. The results show that the AFM can be used to obtain good images of intact and deformed vesicles by tapping mode, as well as to probe the integrity and bilayer structure of the vesicles. AFM force curve compare favorably with other methods to measure mechanical properties of soft samples with higher spatial resolution.     

Formation of aminosilane-functionalized mica for atomic force microscopy imaging of DNA

Factors affecting the functionalization of mica with aminosilanes, in particular, aminopropyltriethoxysilane (APTES-mica), formed from the vapor phase have been systematically studied. The relative humidity (RH) during vapor deposition has been varied, and postdeposition treatment through baking has been used, as well as the comparison of mono and trifunctionality, to investigate how optimal surfaces for AFM imaging of DNA are formed. It is found that the stability of the APTES layers is a consequence of lateral polymerization and not covalent attachment to the mica substrate. At low RH (<25%), DNA adopts an open, well-resolved conformation, whereas at >25% RH, DNA surface-induced condensation occurs. Contact mode AFM scratching experiments show that two main structures of the silane layer exist at different humidity: a monolayer exists at RH < 25%, and a bilayer structure exists at RH > 25%. Finally, structural changes that these two layer types undergo after baking at 150 degrees C were investigated by AFM and X-ray photoelectron spectroscopy (XPS), and these now prevented DNA from binding to the APTES-mica, except in the presence of Mg(II) ions.     

Interaction of small amounts of bovine serum albumin with phospholipid monolayers investigated by surface pressure and atomic force microscopy

The influence of small amounts of bovine serum albumin (BSA) (nM concentration) on the lateral organization of phospholipid monolayers at the air-water interface and transferred onto solid substrates as one-layer Langmuir-Blodgett (LB) films was investigated. The kinetics of adsorption of BSA onto the phospholipid monolayers was monitored with surface pressure isotherms in a Langmuir trough, for the zwitterionic dipalmitoylphosphatidyl ethanolamine (N,N-dimethyl-PE) and the anionic dimyristoylphosphatidic acid (DMPA). A monolayer of N,N-dimethyl-PE or DMPA incorporating BSA was transferred onto a solid substrate using the Langmuir-Blodgett technique. Atomic force microscopy (AFM) images of one-layer LB films displayed protein-phospholipid domains, whose morphology was characterized using dynamic scaling theories to calculate roughness exponents. For DMPA-BSA films the surface is characteristic of self-affine fractals, which may be described with the Kardar-Parisi-Zhang (KPZ) equation. On the other hand, for N,N-dimethyl-PE-BSA films, the results indicate a relatively flat surface within the globule. The height profile and the number and size of globules varied with the type of phospholipid. The overall results, from kinetics of adsorption on Langmuir monolayers and surface morphology in LB films, could be interpreted in terms of the higher affinity of BSA to the anionic DMPA than to the zwitterionic N,N-dimethyl-PE. Furthermore, the effects from such small amounts of BSA in the monolayer point to a cooperative response of DMPA and N,N-dimethyl-PE monolayers to the protein.     

Friction coefficient mapping using the atomic force microscope

A friction coefficient map of the surface of an immiscible polymer blend has been constructed using data obtained with the atomic force microscope. Spatially resolved friction coefficients, obtained from gradients of linear plots of frictional force versus applied load, were used to construct the map, with corresponding frictional forces being derived from lateral force data and the lateral spring constant. Values of the friction coefficient were confirmed using an Si₃N₄/Si₃N₄ couple, for which literature values were available. Excellent agreement with the literature was observed through the use of this method. Copyright © 2004 John Wiley & Sons, Ltd.     

Surface functional group effect on atomic force microscope anodization lithography

The lithographic effect of surface chemical functional groups of organic resists on atomic force microscope (AFM) anodization lithography is investigated using mixed self-assembled monolayers (SAMs). The SAM resist films were prepared with 1,12-diaminododecane dihydrochloride (DAD.2HCl), n-tridecylamine hydrochloride (TDA.HCl), and 1,12-diaminododecane hydrochloride (DAD.HCl), and their film characteristics were evaluated by ellipsometry, zeta-potential measurements, and AFM. The lithographic results indicate that the most dominant factor of the surface functional group effect is the electrochemical property of the surface groups as an anode surface in the anodization reaction, and the dimensions of the protruded patterns are critically determined by the wetting property of the resist surface. By controlling the surface chemical groups with considerations of their effects, high-speed patterning at 2 mm/s was achieved successfully using the mixed SAM resist of DAD.2HCl and TDA.HCl.     

Friction force measurements relevant to de-inking by means of atomic force microscope

In the pulping step of the de-inking process, the ink detaches from the fibers due to shear and physical chemical interaction. In order to get a better understanding of the forces involved between cellulose and ink, the atomic force microscope and the colloidal probe technique have been used in the presence of a model chemical dispersant (hexa-ethyleneglycol mono n-dodecyl ether, C12E6). A cellulose bead was used as the colloidal probe and three different lower surfaces have been used, an alkyd resin, mica and a cellulose sphere. The normal and lateral forces have been measured at a range of nonionic concentrations. It was found that the lateral sliding friction forces deceased with increasing surfactant concentration for both the alkyd resin and mica while no differences were observed for the cellulose surface. In addition, only a very small change in normal force could be detected for the alkyd surface as the concentration changed.     

Compressibility study of quaternary phospholipid blend monolayers

The mechanical properties of liposome membranes are strongly dependent on type and ratio of lipid compounds, which can have important role in drug targeting and release processes when liposome is used as drug carrier. In this work we have used Brewster's angle microscopy to monitor the lateral compression process of lipid monolayers containing as helper lipids either distearoyl phosphatidylethanolamine (DSPE) or dioleoyl phophatidylethanolamine (DOPE) molecules on the Langmuir trough. The compressibility coefficient was determined for lipid blend monolayers containing the helper lipids above, cholesterol, distearoyl phosphatidylcholine (DSPC) and pegylated-DSPE at room temperature. Two variables, the cholesterol fraction and the ratio ρ between the helper lipid (either DSPE or DOPE) and the reference lipid DSPC, were studied by multivariate analysis to evaluate their impact on the compressibility coefficient of the monolayers. The cholesterol level was found to be the most significant variable for DSPE blends while the ratio ρ was the most significant one for DOPE blend monolayers. It was also found that these two variables can exhibit positive interaction and the same compressibility value can be obtained with different blend compositions.     

Direct observation of uncoated spectrin with atomic force microscope

Spectrin molecules extracted from human blood ceil membrane have been examined by atomic force microscopy (AFM) without using shadowing or staining procedures. A drop of the solution containing spectrin molecules was deposited on the freshly deaved mica substrate. After about 1 min, the residual solution was removed with a piece of filter paper. Afterwards the sample was imaged with a home-made atomic force microscope (AFM) in air in a constant force mode. The obtained AFM images revealed that the spectrin molecules prepared from the above procedures exhibit several kinds of structures as follows: (i) the compact rod-like spectrin heterodimers with a length of around 100 nm; (ii) bent or curved linear tetramers with a length of around 200 nm; (iii) somewhat curved spectrin hexamers, octomers or decamers with lengths of about 300, 400, or 500 nm; and (iv) high oligomers with a length above 1 000 nm.     

Hydration of hydrophilic thiolate monolayers visualized by atomic force microscopy

Monolayers of mercaptoundecanol and mercaptoundecanoic acid were prepared on Au(111) films, immersed in aqueous solutions, and probed by frequency-modulation atomic force microscopy. The pN-order tip-surface force was observed over the monolayers as a function of vertical and lateral coordinates, together with the topography of the monolayers. The observed force distribution was modulated between adjacent OH endgroups in the mercaptoundecanol monolayer, as opposed to on top of COOH and COO(-) endgroups in the mercaptoundecanoic acid monolayer. Models of the interfacial hydrogen bond between water and the endgroups were proposed. The force distribution was insensitive to the electrolyte composition. There was no qualitative sign of tip-induced confinement of water.