The influence of micro- and nanoparticles on model atomically flat surfaces on crystallization of polyethylene

Crystallization of high density polyethylene (PE) from the melt on model atomically flat solid surfaces decorated with micro- and nanoparticles of gold or NaCl of different size and densities is investigated. The morphology of the contact layer of PE after its detachment from the support is studied using atomic force microscopy (AFM). It is shown that the nucleating and ordering effect of the solid on PE crystallization depends to a large extend on the nanostructure of its surface, in particular on the size of the atomically flat domains and on the presence of nanoscopic obstacles. The minimum size of the flat domain which can significantly influence the PE crystallization is estimated to be of the order of 150 nm.     

Simultaneous measurement of structural and hydrodynamic forces between colloidal surfaces in complex fluids

An AFM study was performed to measure the effect of approach/retraction speed on the interaction force between a colloidal particle and a flat substrate in aqueous solutions containing silica nanospheres at concentrations of 4.5 and 6.5 vol.%. The total force consisted of contributions of electrostatic, depletion, structural and hydrodynamic forces. The hydrodynamic component of the force could be isolated by comparing the force profiles measured upon approach and retraction. It was found that when the hydrodynamic component was subtracted from the total force, the resulting force profiles measured at scan speeds of 80, 800, 2400, 4800 and 11,200 nm/s all overlaid, indicating that the surface forces (electrostatic, depletion and structural) were not affected by the scan speed. This result was further supported by an approximation of the rates of viscous and diffusive motion in the gap region. In addition, the variation of the hydrodynamic force with particle/plate separation distance agreed relatively well with a prediction made using the mobility correction factor developed for simple fluids, suggesting that the nanoparaticles do not alter the flow in the lubrication layer at these concentrations.     

Microscopy of large-scale porphyrin aggregates formed from protonated TPP dimers in water–organic solutions

Properties of porphyrin aggregates were investigated by absorption spectroscopy (UV–Vis and IR) in water–tetrahydrofuran (THF) solutions in the presence of different concentrations of HCl. The morphology of the aggregates was observed by scanning electron microscopy (SEM) and atomic force microscopy in thin films. A new protonated meso-tetraphenylporphine (TPP) form that shows characteristic absorptions in the UV–Vis spectra was found in the aggregated porphyrin in the presence of 2N HCl. Two types of changes with time were observed in these spectra, one of which is due to sticking together of the porphyrin aggregates. The second is associated with the formation of complexes between the protonated TPP dimer with λ_max=465 nm and metal ions that are probably leached out from the support by the acid. IR spectra of porphyrin aggregates prepared in the presence of different concentrations of HCl show huge water contents in the thin films and different characteristics of the water bound in the aggregates. Porphyrin aggregates prepared at different concentrations of HCl exhibited different surface properties. TPP aggregates prepared in the presence of 0.4N HCl and observed by SEM exhibit smooth surfaces over ranges of several micrometers. TPP aggregates prepared in the presence of 2N HCl form a continuous thin layer with 3–5 μm wide domains that consist of submicroscopic grains. These appear to be the result of 200–400 nm wide spherical particles that stick together.     

Nanomanipulation of extended single-DNA molecules on modified mica surfaces using the atomic force microscopy

The technique of nanometer scale manipulation is very important in constructing nano-structures and nano-devices. By using atomic force microscope, three kinds of controllable manipulation on single-DNA molecules were introduced in the paper. DNA molecules deposited and extended on modified mica surface were first imaged by tapping mode, then cutting, bending, and pushing were respectively performed on single-DNA molecules. The results of the manipulation depend on the interaction between tip and DNA as well as between substrate and DNA.     

血卟啉在胶束介质中的聚集状态研究

用光谱法研究了光敏剂血卟啉在水溶液中的聚集状态，并以胶束作为生物膜模型，探讨了血卟啉在胶束介质中的聚集状态状态变化，用原子力显微镜研究了血卟啉聚集状态的微观结构及其在胶束介质中的聚集状态。     

AFM of adsorbed polyelectrolytes on cellulose I surfaces spin-coated on silicon wafers

Thin layers of cellulose I nanocrystals were spin-coated onto silicon wafers to give a flat model cellulose surface. A mild heat treatment was required to stabilize the cellulose layer. Interactions of this surface with polyelectrolyte layers and multilayers were probed by atomic force microscopy in water and dilute salt solutions. Deflection–distance curves for standard silicon nitride tips were measured for silicon, cellulose-coated silicon, and for polyelectrolytes adsorbed on the cellulose surface. Transfer of polymer to the tip was checked by running deflection–distance curves against clean silicon. Deflection–distance curves were relatively insensitive to adsorbed polyelectrolyte, but salt addition caused transfer of cationic polyelectrolyte to the tip, and swelling of the polyelectrolyte multilayers.     

Nanoscale evaluation of lubricity on well-defined polymer brush surfaces using QCM-D and AFM

For preparing a “highly lubricated biointerface”, which has both excellent lubricity and biocompatibility, we investigated the factors responsible for resistance to friction during polymer grafting. We prepared poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(methyl methacrylate) (PMMA) brush layers with high graft density and well-controlled thickness using atom transfer radical polymerization (ATRP). We measured the water absorptivity in the polymer brush layers and the viscoelasticity of the polymer-hydrated layers using a quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The PMPC brush layer had the highest water absorptivity, while the PMPC-hydrated layer had the highest fluidity. The friction properties of the polymer brush layers were determined in air, water, and toluene by atomic force microscopy (AFM). The friction on each polymer brush decreased only when a good solvent was chosen for each polymer. In conclusion, the brush layer possessing high water absorptivity and fluidity in water contributes to reduce friction. PMPC grafting is an effective and promising method for obtaining highly lubricated biointerfaces.     

Kinetic studies on the interactions between glycolipid biosurfactant assembled monolayers and various classes of immunoglobulins using surface plasmon resonance

Kinetic studies on the interactions between self-assembled monolayers of mannosylerythritol lipids (MELs), which are glycolipid biosurfactants abundantly produced by microorganisms, and various classes of immunoglobulins including human IgG, IgA, and IgM were performed using surface plasmon resonance (SPR). The effect of the MEL structure on the binding behavior of HIgG was examined. Assembled monolayers of MEL-A having two acetyl groups on the headgroup gave a high affinity (K_d = 1.7 × 10⁻⁶ M) toward HIgG, while those of MEL-B or MEL-C having only one acetyl group at C-6′ or C-4′ position gave little affinity. Our kinetic analysis revealed that the binding manner of HIgG, HIgA (K_d = 2.4 × 10⁻⁷ M), and HIgM (K_d = 2.2 × 10⁻⁷ M) to the assembled monolayers of MEL-A is not the monovalent mode but the bivalent mode, and both the first and second rate association constants (k_a1, k_a2) increase with an increase in the number of antibody binding sites, while those for dissociation (k_d1, k_d2) changed little. Moreover, we succeeded in directly observing great amounts of HIgG, HIgA, and HIgM bound to MEL-A monolayers using atomic force microscopy (AFM). Finally, we found that MEL-A assembled monolayer binds toward various IgG derived from mouse, pig, rabbit, horse, goat, rat, and bovine as well as human IgG (HIgG), and the only exception was sheep IgG. These results clearly demonstrate that MEL-A assembled monolayers would be useful as noble affinity ligand system for various immunoglobulins.     

Selective recognition of organic pollutants in aqueous solutions with composite imprinted membranes

In this work, thin-layer composite membranes imprinted with desmetryn or ibuprofen were prepared and studied for selective recognition of the template compounds in aqueous solutions. The imprinted membranes were developed using photoinitiated copolymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid and N,N'-methylene-bis-acrylamide, in the presence of desmetryn or via copolymerization of dimethylaminoethyl methacrylate, and trimethylopropane trimethacrylate, in the presence of ibuprofen, followed by deposition of the imprinted layers on the surface of porous microfiltration supports of various chemical nature. Atomic force microscopy was used to study the surface morphological characteristics of the developed membranes. Molecularly recognition properties of imprinted membranes were evaluated by measuring their capability to bind the template molecules from polycomponent aqueous solutions. It was shown that obtained membranes may be used as selective recognising elements of portative differential capacitor sensor device for express monitoring of the target molecules in water. The sensor performance is based on registration of the alteration of dielectric permeability of composite imprinted membrane at selective binding of template molecules, when the analyzed feed solution is filtered through the membrane sample.     

Prediction of the surface tension of mixed electrolyte solutions based on the equation of Patwardhan and Kumar and the fundamental Butler equations

The predictive equation of Patwardhan and Kumar for the water activity of mixed electrolyte solutions has been used together with the fundamental Butler equations to establish a new simple predictive equation for the surface tension of mixed electrolyte solutions. This newly proposed equation can provide the surface tensions of multicomponent solutions using only the data of the corresponding binary subsystems of equal ionic strength. No binary interaction parameters are required. The predictive capability of the equation has been tested with the experimental data for 26 concentrated multicomponent electrolyte solutions at different temperatures and compared with the model of Li et al. Both equations agree well with the experimental results of systems examined over entire experimental composition ranges, but the new equation generally gives better predictions for most 1:1 electrolyte systems examined, and considerable improvement in predictions has been achieved for all the mixtures containing 1:2 and 2:2 electrolytes and for 1:1 electrolyte systems at higher temperatures.     

Controlled synthesis of hydrophilic concentrated polymer brushes and their friction/lubrication properties in aqueous solutions

Polymer brushes of water‐soluble polymers, poly(2‐hydroxyethyl acrylate) (PHEA) and poly(poly(oxyethyleneglycol)methylether acrylate) (PPEGA), were synthesized on a silicon wafer and a silica particle by applying photo‐induced organotellurium‐mediated radical polymerization to surface‐initiated graft polymerization. High graft densities were obtained, corresponding to reduced graft densities of about 0.32 and 0.42 for the PHEA and PPEGA brushes, respectively. These values were high enough to be categorized in the regime of “concentrated” polymer brushes (CPBs). Atomic force microscopic (AFM) study revealed that the CPB of PPEGA was allowed to be highly swollen in water but the CPB of PHEA did not. This means that water is reasonably good for PPEGA but not for PHEA. The AFM microtribological study between swollen brushes revealed two lubrication regimes, namely, boundary‐ and hydrodynamic‐lubrication regimes, with different shear‐velocity dependencies. Reflecting insufficient quality of water as a solvent, the CPB of PHEA showed adhesive interaction and thereby a higher frictional coefficient μ in the boundary lubrication. More interestingly, super lubrication was achieved for the CPB of PPEGA with a μ value in the order of 10^?4 in water and in 0.1 M aqueous NaCl solution (without the help of electrostatic repulsion). Super lubrication was concluded to be a characteristic feature of the CPB, even in an aqueous system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

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     

原子力显微镜在多糖结构研究中的进展

简述了原子力显微镜(AFM)的工作原理和特点,以及在多糖,特别是在淀粉结构研究中的进展。     

A combined TEM and SKPFM investigation of the surface layers on rolled AA5050 aluminium alloy using ultra‐microtomy

This article studies the evolution of near‐surface morphology as a function of various thermo‐mechanical treatments along the fabrication line of rolled AA5050 aluminium alloy. Ultra‐microtomy has been used to prepare cross‐sectional thin foils for transmission electron microscopy (TEM) and proper surfaces for scanning Kelvin probe force microscopy (SKPFM) analysis. A slight increase in the Volta potential difference (between the inter‐metallics and the matrix) between the as‐cast surface and the surface obtained after the first hot‐mill pass, emphasized that the changes in surface micro‐structure, which in turn affect the corrosion and electrochemical properties of the finished product, had already occurred at that stage. The Volta potential difference during the subsequent hot‐mill pass remained relatively constant. As far as the near‐surface morphology was concerned, hot‐rolling resulted in the formation of a heavily deformed surface layer. Annealing of the hot‐rolled aluminium sheet resulted in partial re‐crystallization of the surface layer. Subsequent cold‐rolling re‐introduced deformation in the near‐surface region. Copyright © 2008 John Wiley & Sons, Ltd.     

Thickness and morphology of polyelectrolyte coatings on silica surfaces before and after protein exposure studied by atomic force microscopy

Analyte–wall interaction is a significant problem in capillary electrophoresis (CE) as it may compromise separation efficiencies and migration time repeatability. In CE, self-assembled polyelectrolyte multilayer films of Polybrene (PB) and dextran sulfate (DS) or poly(vinylsulfonic acid) (PVS) have been used to coat the capillary inner wall and thereby prevent analyte adsorption. In this study, atomic force microscopy (AFM) was employed to investigate the layer thickness and surface morphology of monolayer (PB), bilayer, (PB-DS and PB-PVS), and trilayer (PB-DS-PB and PB-PVS-PB) coatings on glass surfaces. AFM nanoshaving experiments providing height distributions demonstrated that the coating procedures led to average layer thicknesses between 1 nm (PB) and 5 nm (PB-DS-PB), suggesting the individual polyelectrolytes adhere flat on the silica surface. Investigation of the surface morphology of the different coatings by AFM revealed that the PB coating does not completely cover the silica surface, whereas full coverage was observed for the trilayer coatings. The DS-containing coatings appeared on average 1 nm thicker than the corresponding PVS-containing coatings, which could be attributed to the molecular structure of the anionic polymers applied. Upon exposure to the basic protein cytochrome c, AFM measurements showed an increase of the layer thickness for bare (3.1 nm) and PB-DS-coated (4.6 nm) silica, indicating substantial protein adsorption. In contrast, a very small or no increase of the layer thickness was observed for the PB and PB-DS-PB coatings, demonstrating their effectiveness against protein adsorption. The AFM results are consistent with earlier obtained CE data obtained for proteins using the same polyelectrolyte coatings.     

Investigation on the folding mode of a polymer chain in a spiral crystal by single molecule force spectroscopy

Investigation on the folding mode of a single polymer chain in its crystal is significant to the understanding of the mechanism of the fundamental crystallization as well as the engineering of new polymer crystal-based materials. Herein, we use the combined techniques of atomic force microscopy （AFM） imaging and force spectroscopy to pull a single polyethylene oxide （PEO） chain out of its spiral crystal in amyl acetate. From these data, the folding mode of polymer chains in the spiral crystal has been reconstructed. We find that the stems tilt in the typical flat area, leading to the decrease in the apparent lamellar height. While in the area of screw dislocation, the lamellar height gradually increases in the range of several nanometers. These results indicate that the combined techniques present a novel tool to directly unravel the chain folding mode of spiral crystals at single-molecule level.     

Synthesis of novel hybrid films of a layered silicate and alkylammonium cations on rough polymeric surfaces by Langmuir–Blodgett method

Hybrid films of a layered silicate and an amphiphilic alkylammonium (hexadecyltrimethylammonium) cation have been prepared by Langmuir–Blodgett (LB) method and transferred onto a polyamide surface by dip coating. This is the first time that stable LB hybrid monolayer and multilayer films have been formed on rough polymeric surfaces. The films were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and water contact angle measurements. XRD and FTIR showed that the hybrid multilayer was well-organized and the thickness of one layer was calculated to be 1.6 nm. Furthermore, the layered silicate was determined to be on the substrate side and the amphiphilic molecule layer was exposed to the air side. This provides a novel methodology for the surface modification of polymers.     

基于AFM的药物刺激前后淋巴瘤活细胞的形貌及弹性的变化

原子力显微镜(AFM)的发明为研究单个活细胞的形貌结构及物理特性提供了新的技术手段.然而,由于缺少合适的固定方法,利用AFM对动物悬浮活细胞的形貌进行高分辨率成像还面临着巨大的挑战.本文提出一种基于微柱阵列和静电吸附相结合的动物悬浮细胞固定方法.通过微柱阵列的机械钳制和多聚赖氨酸的静电吸附实现了对单个淋巴瘤B细胞的固定,并在此基础上利用AFM动态观测了不同浓度Rituximab刺激下淋巴瘤B细胞的表面形貌及弹性的变化.经过0.2 mg·mL-1的Rituximab刺激2 h后,细胞表面的褶皱增加,细胞的杨氏模量从196 kPa减小到183 kPa.经过0.5 mg·mL-1的Rituximab刺激2 h后,细胞形貌发生显著变化并出现突起结构,细胞的杨氏模量从234 kPa减小到175 kPa.实验结果表明淋巴瘤细胞形貌和弹性变化的幅度随着Rituximab刺激浓度的增加而增加,加深了对Rituximab作用效果的认识.     

Oxidation of Electrodeposited Copper on Boron Doped Diamond in Acidic Solution: Manipulating the Size of Copper Nanoparticles Using Voltammetry

The in situ deposition of copper, in acidic solution onto a Boron Doped Diamond electrode, using cyclic voltammetry is explored and produced surfaces are imaged using Atomic Force Microscopy. A uniformly dense covering of copper nanoparticles is produced when the potential of a freshly polished BDD electrode is swept from 0 V in a negative direction. For example, in 1 M H₂SO₄ with a Cu(II) concentration of 1 mM, nanoparticles of height 10.1 nm, diameter 74.6 nm and a density of 16.1 particles per μm² are created when the potential is swept to ?0.35 V. The higher the concentration of Cu(II) in solution or the larger the magnitude of the end potential the larger the nanoparticles are and the more densely they are spread. When the direction of the scan is reversed and a positive potential sweep carried out evidence from the observed cyclic voltammograms and AFM images shows that copper is being incompletely stripped from the electrode surface. If the potential is then cycled continuously ten times, as would happen when the process is used for electroanalytical purposes, then an irregular and irreproducible deposit is observed. One can infer from this evidence that the incompletely stripped copper is electrochemically active and therefore adversely affecting subsequent deposition processes. Comparison to existing literature shows that the discrete application of particular deposition and stripping potentials is a much better way to produce a deposit of copper nanoparticles than application of potential through cyclic voltammetry.     

Atomic force microscopy study of salivary pellicles formed on enamel and glass in vivo

This study was performed to evaluate the use of atomic force microscopy (AFM) in examining the surface of the adsorbed layer of salivary proteins (salivary pellicle) formed in vivo on dental enamel and glass surfaces. Enamel and glass test pieces were attached to the buccal surfaces of the upper first molar teeth in two adults using removable intraoral splints. The splints were carried intraorally over periods ranging from 10 min to1 h. Using the contact mode of AFM, pellicle structures could be recognised on intraorally exposed specimens compared to nonexposed enamel and glass surfaces. The surface of the adsorbed salivary pellicle was characterised by a dense globular appearance. The diameter of the globulelike protein aggregates adsorbed onto enamel and glass varied between 80 and 200 nm and 80 and 150 nm, respectively. The structure of the adsorbed protein layer was clearly visible on glass surfaces, even though minor differences in the protein layer between glass and enamel specimens were observed. This study indicates that AFM is a powerful tool for high-resolution examination of the salivary pellicle surface structure in its native (hydrated) state. AFM avoids artefacts due to fixing, dehydration and sputter-coating which occur with scanning electron microscopic analyses. Received: 29 November 2000 Accepted: 14 December 2000