Electrochemical study of the diffusion of cytochrome c within nanoscale pores derived from cylinder-forming polystyrene-poly(methylmethacrylate) diblock copolymers

This paper reports cyclic voltammograms of cytochrome c on recessed nanodisk-array electrodes (RNEs) based on nanoporous films (11, 14 or 24 nm in average pore diameter; 30 nm thick) derived from polystyrene-poly(methylmethacrylate) diblock copolymers. The faradic current of cytochrome c was observed on RNEs, indicating the penetration of cytochrome c (hydrodynamic diameter ≈ 4 nm) through the nanopores to the underlying electrodes. The faradic current on RNEs with 11- and 14-nm nanopores mainly originated from cytochrome c adsorbed on the underlying electrodes, whereas the current on RNEs with 24-nm pores was diffusion-controlled. Interestingly, the diffusion-controlled current of cytochrome c was significantly smaller than that estimated from the faradic current of 1,1′-ferrocenedimethanol on the RNEs. The smaller faradic current suggested more effective decrease in the diffusion coefficient of cytochrome c as compared to that of 1,1′-ferrocenedimethanol, which probably reflected enhanced steric and chemical interactions within the nanopores. Comparison between experimental data and results of finite-element computer simulations made it possible to assess the structure of the nanoporous films and the diffusion coefficients of redox species within the nanopores.     

Surface crystallization of poly(ethylene terephtalate) studied by atomic force microscopy

Poly(ethylene terephtalate) (PET) crystallization was shown by atomic force microscopy (AFM) to occur at 85 °C in the first few nanometers near the polymer-air interface. The surface was fully transformed into spherulites after 30 min, while no signs of bulk crystallization were observed by FTIR. All the observed spherulites presented a nucleation centre, indicating that the crystallization process started at the surface of the film. Tapping mode AFM confirmed that the spherulites were not covered by an amorphous layer. The most probable explanation is a decrease of T_g near the surface. Due to the poor crystallization conditions, the constitutive units of the spherulites were small crystalline blocks. By changing the annealing time, it was possible to produce PET surfaces with different surface fractions consisting of semi-crystalline material (spherulites) and amorphous matrix. This provided a controlled surface heterogeneity on the submicrometer scale, with a contrast in terms of stiffness, roughness and swelling by organic solvents.     

Study on the adsorption of poly(o-ethoxyaniline) nanostructured films using atomic force microscopy

Nanostructured films of poly(o-ethoxyaniline) (POEA) were studied by atomic force microscopy (AFM), which indicated a globular morphology for films containing one or more layers of POEA. Consistent with the nucleation and growth model for the adsorption process, the mean roughness and fractal dimension were found to increase with the time of adsorption and with the number of POEA layers in the initial stages of adsorption, reached maximum values and then decreased after 10 min of adsorption or after deposition of five POEA layers. Such behavior has been explained in terms of the decrease in the film irregularities, with voids being filled with polymeric material leading to smoother surfaces.     

An atomic force microscopy study of ozone etching of a polystyrene/polyisoprene block copolymer

The ozone etching of a commercial poly(styrene)/poly(isoprene) (PS/PI) block copolymer (Kraton D1117) was studied by atomic force microscopy. The copolymer contains 17% PS and forms a cylindrical phase in the melt. The copolymer dewetted when spin coated onto a silicon wafer but the film was stable on a grown silicon oxide layer. The structure of the stripe pattern formed was examined on substrates with different oxide layer thicknesses (surface energies). Finally etching by ozone was investigated. For low ozone doses, no degradation of polymer was observable. Extended ozone treatment resulted in more obvious degradation, but the etching was non-selective.     

Lamellar morphology of random metallocene propylene copolymers studied by atomic force microscopy

Four sets of propylene based random copolymers with co-units of ethylene, 1-butene, 1-hexene and 1-octene, and a total defect content up to ∼9 mol% (including co-unit and other defects), were studied after rapid and isothermal crystallization. Etched film surfaces and ultramicrotomed plaques were imaged so as to enhance contrast and minimize catalyst and co-catalyst residues. While increasing concentration of structural irregularities breaks down spherulitic habits, the formation of the gamma polymorph has a profound effect on the lamellar morphology. Lamellae grown in the radial axis of the spherulite and branches hereon are replaced in γ-rich copolymers with a dense array of short lamellae transverse or tilted to the main structural growth axis. This is the expected orientation for γ iPP branching from α seeds. Spherulites are formed in copolymers with non-crystallizable units (1-hexene and 1-octene) up to ∼3 mol% total defect content and were observed up to ∼6 mol% in those with partially crystallizable comonomers (ethylene and 1-butene). However, lamellae were observed in all the copolymers analyzed, even in the most defective ones, highlighting the important role of the gamma polymorph in propagating lamellar crystallites in poly(propylenes) with a high concentration of defects. Long periods measured from AFM and SAXS are comparatively analyzed.     

Aggregation properties of amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer studied by cyclic voltammetry

The cyclic voltammetric behaviors at a platinum electrode of an amphiphilic block copolymer [poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (F127)] in aqueous solutions were investigated. The mechanism of the electrochemical reaction of F127 at a platinum electrode was deduced. The diffusion coefficients of different-shaped aggregates formed by F127 were determined on this basis. The first and second critical micelle concentrations, corresponding to the formation of spherical micelles and the transition of the spherical to rod-like micelles, were 3.72×10⁻⁴ mol·L⁻¹ and 1.49×10⁻³ mol·L⁻¹, respectively, which could be confirmed by the fluorescent anisotropy of pyrene in the F127 aggregates and the morphology of F127 micelles observed by freeze-fracture transmission electron microscopy.     

Microphase separation and crystallization in mixtures of polystyrene-poly(methyl methacrylate) diblock copolymer and poly(vinylidene fluoride)

This study examined the microdomain structures and the crystallization behavior in binary blends consisting of an asymmetric block copolymer and a homopolymer using small-angle X-ray scattering, optical microscopy and differential scanning calorimetry. A polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) was mixed with a low molecular weight poly(vinylidene fluoride) (PVDF), where the PS-b-PMMA had a 0.30 wt fraction of the PMMA block. At a PVDF concentration of <13.0 wt%, the PVDF was completely miscible with the PMMA microdomains, and the blends had a cylindrical structure. The addition of PVDF altered the morphology from a PMMA-cylindrical structure to a lamellar structure and finally to a PS-cylindrical structure. When the PVDF concentration was <23.0 wt%, the PVDF was distributed uniformly within the PMMA microdomains. After adding more PVDF, some of the PVDF was locally dissolved in the middle of the PMMA microdomains. The addition of PVDF also affected the ordered microstructure in the blends, leading to a well-defined microdomain structure. However, PVDF crystallization significantly disturbed the pre-existing microdomain structure, resulting in a poorly ordered morphology. In the blends, PVDF had unique crystallization behavior as a result of the space constraints imposed by the microdomains.     

The ultrastructure of spruce kraft pulps studied by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS)

Surface properties of spruce (Picea abies) kraft pulps cooked for different times and further OD₀E₁D₁E₂D₂-bleached were investigated with atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). A rough correlation between the increasing relative amount of the fibrillar surface structure in AFM images and increasing O/C atomic ratio in XPS-spectra was found with proceeding delignification. At the end of cooking (120 min) only about 1/3 of the fibre surface consisted of cellulose. The detailed analysis of the relative peak areas of the different C1s components in the XPS-spectra indicated that the granules at the beginning of cooking at 170 °C consisted mainly of lignin and extractives. The analysis also showed that different steps of the bleaching sequence were quite specific in removing structural components. Furthermore, the lignin removal was shown not to result automatically in increased fraction of exposed cellulose surface, but could also lead in increased relative amount of surface extractives. Evidence for the high surface content of hemicelluloses for the D2-stage sample was observed. Hemicelluloses with both fibrillar and amorphous morphology were found to be present.     

Micromorphological characterization of polymer-oxide nanocomposite thin films by atomic force microscopy and fractal geometry analysis

The purpose of this study was to evaluate the 3-D surface micromorphology of polymer-oxide thin films spin-coated from a composite of poly-methyl-methacrylate as the matrix and elongated titania nanorods as the filler particles. The surfaces of these composite films were investigated by atomic force microscopy and characterized by fractal geometry analysis. The effect of increasing loading of the fillers between 0 and 30% by weigth relative to the matrix was assessed. An increasing roughness was observed, with typical emergence of protruding ripples progressively extending into larger stripes. The amplitude parameters of the surfaces were determined by analysis of the height distributions. The fractal analysis of roughness revealed that the films have fractal geometry. Triangulation method based on the linear interpolation type was applied to determine the fractal dimension. A connection was observed between the surface morphology and the physical properties of the coatings as assessed in previous works.     

Atomic force microscopy study of comb-like vs. arborescent graft copolymers in thin films

This work deals with the study of comb-like vs. arborescent grafted copolymers made of poly(chloroethyl vinyl ether)-g-polystyrene (PCEVE-g-PS). We describe how the molecular architecture of the branched polymers affects their nanoscale organization in thin films, as observed using atomic force microscopy. The results indicate that modifying the molecular architecture from a ‘generation-zero’ comb-like (PCEVE-g-PS) to a ‘first-generation’ hyperbranched (PCEVE-g-(PS-b-PCEVE-g-PS)) architecture strongly modifies the observed geometrical parameters of the molecules, in good agreement with the expected evolution of the molecular dimensions and the corresponding data obtained in solution.The surface organization of the (PCEVE-g-PS) copolymer molecules is also strongly conditioned by the interplay between the molecule-substrate interactions and the molecule-molecule interactions, leading to different possible orientations of the lateral branches with respect to the surface and thus to different final morphologies.     

Perpendicular lamellae induced at the interface of neutral self-assembled monolayers in thin diblock copolymer films

We obtained perpendicular lamellar orientations in thin films of symmetric polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, on self-assembled monolayers (SAMs) of 3-(p-methoxyphenyl)propyltrichlorosilane (MPTS) prepared on silicon wafers. In contrast to completely parallel lamellae on silicon wafers having a native oxide layer, perpendicular lamellae at the MPTS interface with parallel lamellae at the air interface were directly observed by transmission electron microscopy (TEM) in cross-sectional view. The perpendicular lamellae at the MPTS interface were attributed to the non-preferential (neutral) MPTS-covered substrate to both PS and PMMA blocks. The neutrality of the SAMs of MPTS was confirmed by the similar interfacial tension values of the SAMs of MPTS with PS and PMMA, estimated by contact angle measurements.     

Surface structure of Kevlar® fiber studied by atomic force microscopy and inverse gas chromatography

Kevlar® fiber surface structure was primarily and directly observed in the filament configuration by the tapping mode atomic force microscopy (AFM). The microfibrils feature was observed with an average width of 500 nm, composed of various types of periodical units of an average size 50 nm in a pleating appearance. At the less crystalline spot on the Kevlar® fiber surface, the periodical organizations exhibit the skin-core-like differentiation. In contrast, at the highly crystalline spot, the periodicity is more uniformly arranged by a rectangular network manner. Inverse gas chromatography (IGC) was used as a tool to investigate the surface structure heterogeneity by calculating the surface energy of different types of probes adsorbed on the Kevlar® fiber surface. The energy sites distribution plot of n-hexylamine adsorption at finite dilution exhibits a two-adsorbing-peaks curve. At the higher energy site, a possible hydrogen-bonding interaction was proposed between n-hexylamine and oxygen-containing groups formed at the less crystalline surface. According to the AFM and IGC results, a Kevlar® fiber surface organizations model at the nanometer scale was proposed.     

Self‐assembled multilayer films based on diazoresins studied by atomic force microscopy/friction force microscopy

The layer‐by‐layer self‐assembled NDR‐PSS (nitro‐containing diazoresin‐polysodium p‐styrenesulfonate) films were fabricated. The crosslinking structure formed from the conversion of ionic bond to covalent bond after UV irradiation, confirmed by small angle X‐ray diffraction. The roughness and microtribological properties of NDR‐PSS films were investigated by atomic force microscopy/friction force microscopy. The ordered multilayer films after photoreaction are better in microtribological performance than that of the monolayer film. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 631–638, 2000     

In situ atomic force microscopy of the melting of melt-crystallized polyethylene

High temperature AFM is used to observe the melting of polyethylene lamellae crystallized from the melt in situ in real-time. Both oriented and un-oriented samples are observed. The melting of shish-kebab structures, including revealing the bare oriented shish, is achieved. Lamellae are observed to melt from their edges, and this is proposed to be due to the inherent higher mobility at the crystal edges rather than differences in stability within the crystal due to different levels of post crystallization perfecting. Observation of the melting of structures that have been observed during growth confirms that material crystallized at lower temperatures melts first, followed by material crystallized in confined geometries, and finally the rest of the isothermally crystallized lamellae that melt back from the edges with an apparently random morphology that is not the reverse of the growth process. In situ observation during melting is confirmed as an alternative and complementary technique to etching to reveal behaviour during crystallization when crystallization is too rapid for in situ observation.     

Introducing open films of nanosized cellulose—atomic force microscopy and quantification of morphology

A method for preparing open, sub-monolayer cellulose films on a silicon substrate is introduced, and the open films were quantified using the three-dimensional information from atomic force microscopy (AFM) height images. The preparation method is based on spin coating low concentrations of trimethylsilyl cellulose (TMSC) on silicon and hydrolysing the TMSC to cellulose using a vapour phase acid hydrolysis. AFM showed that the surfaces consist of nanosized cellulose patches which are roughly 50-100 nm long, 20 nm wide, and 1 nm high. The volume of the cellulose patches was quantified. Examination of the cross section of the cellulose patches revealed that the exaggeration of the lateral dimensions by the AFM tip is small enough to account for a mere ±2% error in the volume quantification. Pilot experiments showed that the volume of the cellulose was largely restored in a wetting/drying cycle but the morphology changed considerably. Because of their small size, the cellulose patches provide a novel approach for interpretation on the molecular architecture of cellulose.     

Metallo-functionalized first-generation salicylaldimine poly(propylenimine) tetraamine dendrimers: Electrochemical study and atomic force microscopy imaging

The adsorption and the redox processes of two first-generation salicylaldiamine dendritic ligands and their copper, cobalt and nickel metallo-functionalized complexes have been studied at two types of carbon electrode surface. Glassy carbon (GC) was used in an electrochemistry study and highly oriented pyrolitic graphite (HOPG) in ex situ atomic force microscopy (AFM) imaging. All salicylaldimine ligands and their metallo-functionalized complexes adsorb on the surface of the HOPG electrode, resulting in the formation of nanoclusters and films, which vary between 0.9 and 6 nm in size, depending on the metallo-functionalized salicylaldimine dendrimer chemical composition and solution concentration. Differential pulse voltammetry of the surface-confined films has shown that the anodic reactions observed correspond to the oxidation of the hydroxyl groups present in the ligand structure of all compounds. However, by following the changes in peak currents, potentials and width at half height it has been shown that destabilization of the ligand internal structure occurred in the metallo-functionalized complexes depending on the metal involved. The electrochemical behaviour of the surface-confined films observed in buffer solution was related to the morphology, obtained by AFM, of the immobilised first-generation salicylaldiamine dendritic ligands and corresponding salicylaldimine metallo-functionalized complexes.     

Effects of additives on the morphologies of thin titania films from self-assembly of a block copolymer

The effects of additives of poly(methyl methacrylate) (PMMA) and HAuCl₄ on the morphologies of hybrid titania films formed via co-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) copolymers, titania sol-gel precursor in a selective solvent were investigated. The results show that addition of PMMA or HAuCl₄ has an important influence on the morphologies of hybrid titania films. Addition of PMMA or HAuCl₄ can induce the morphology transition of the PS-b-PEO/titania sol-gel mixture from spherical micelles to vesicles. Therefore, the morphologies of the hybrid films formed on silicon substrate surfaces by spin-coating can be controlled by the addition of homopolymer (PMMA) or inorganic precursor (HAuCl₄) into the PS-b-PEO/titania sol-gel mixtures, allowing access to nanoparticles or nanoporous films. After removing the polymer matrix, nanoparticle aggregates or nanobowl-like structures are left behind on the substrate surfaces.     

Effect of nanoparticle surface functionality on microdomain orientation in block copolymer thin films under electric field

The electric field induced microdomain orientations has been an interesting research topic. In this article, the effect of nanoparticle surface functionality on microdomain alignments in block copolymer/nanoparticle hybrid thin films was investigated with transmission electron microscopy experiments. The presence of gold nanoparticles influenced the microdomain orientation behaviors of block copolymer/nanoparticle thin films. The possibility for complete alignment normal to the substrate was illustrated by controlling electric field strength, concentration, and surface ligands of nanoparticles. This work provides basic and essential data to understand the properties and behaviors of emerging block copolymer/nanoparticle hybrid thin films.     

In-situ atomic force microscopy of silicon(100) in aqueous potassium hydroxide

Growth dynamics of pyramid-shaped features that emerge during etching of silicon(100) surfaces in 2 M aqueous potassium hydroxide solutions have been investigated using in-situ atomic force microscopy. Micropyramids were found to grow continuously from a scale-shaped structure that is present on the surface during etching. In addition, two characteristic removal mechanisms of fully developed pyramids could be identified. It is suggested that these etching mechanisms are unique to pyramids and not comparable to the etching properties of single crystal surfaces.