Implementation of NSOM to biological samples

Near-field scanning optical microscopy is a technique providing images of structures with spatial resolution better than $\lambda/2$, which is undetectable in far-field where the Abbe law of limiting resolution is critical. In parallel to the optical imaging, topography maps are also acquired. Near-field scanning optical microscopy measurements can be performed both in air and liquid environments. The later makes the technique very useful for biomaterials analysis offering information that could not be obtained with other methods. Our work presents the results of recent studies on application of near-field scanning optical microscopy to imaging of cells in air as well as in physiological buffers. Differences in cell's topography and morphology have been noticed between two cell lines from human bladder non-malignant (HCV29) and malignant (T24) cancers. Presented results are part of the research that characterizes physiological changes of cells depending on stage of cancer

Precise positioning of cancerous cells on PDMS substrates with gradients of elasticity

In this work the novel method to create PDMS substrates with continuous and discrete elasticity gradients of different shapes and dimensions over the large areas was introduced. Elastic properties of the sample were traced using force spectroscopy (FS) and quantitative imaging (QI) mode of atomic force microscopy (AFM). Then, fluorescence microscopy was applied to investigate the effect of elastic properties on proliferation of bladder cancer cells (HCV29). Obtained results show that cancerous cells proliferate significantly more effective on soft PDMS, whereas the stiff one is almost cell-repellant. This strong impact of substrate elasticity on cellular behavior is driving force enabling precise positioning of cells

Elasticity patterns induced by phase-separation in polymer blend films

Systematical studies on the impact of the thickness of thin films composed of polystyrene (PS) or poly(ethylene oxide) (PEO) on the effective elasticity of polymer-decorated soft polydimethylsiloxane substrate were performed. For both investigated polymer films, elasticity parameter was determined from force-displacement curves recorded using atomic force microscopy. Effective stiffness of supported film grows monotonically with film thickness, starting from the value comparable to the elasticity of soft support and reaching plateau for polymer layers thicker than 200 nm. In contrary, for films cast on hard support no significant thickness dependence of elasticity was observed and the value of elasticity parameter was similar to the one of the substrate. Based on these results, non-conventional method to produce elasticity patterns of various shapes and dimensions induced by phase-separation process in symmetric and asymmetric PS:PEO blend films on soft support was demonstrated. Elevated PS domains were characterized by elasticity parameter 2 times higher than lower PEO matrix. In contrary, adhesion force was increased more than 3 times for PEO regions, as compared to PS areas

Self-assembly of terephthalic acid on rutile TiO2(110): toward chemically functionalized metal oxide surfaces

Self-organization of 1,4-benzenedicarboxylic acid molecules (terephthalic acid, TPA) on a rutile TiO2(110)-(1×1) surface is studied by means of ultra-high vacuum scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). When saturation coverage is achieved with the formation of one monolayer, STM images reveal two alternating contrast patterns: (i) a well-organized (2×1) structure and (ii) a mixed structure of molecular rows oriented along the 001 crystallographic direction. Complementary STM images recorded with two different tip terminations prove that the two contrasting patterns indicate the same stable surface structure. The nc-AFM imaging confirms the mixed molecular row structure. It is concluded that TPA molecules are adsorbed in an upright position. This occurs with one of the carboxyl group bound dissociatively in a bi-dentate fashion with the two 5-fold coordinated Ti atoms. The second carboxyl group is exposed to the vacuum interface. This carboxyl terminated surface is discussed in terms of surface chemical functionalization

Transformations of PTCDA structures on rutile TiO2 induced by thermal annealing and intermolecular forces

Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed

High-resolution STM studies of terephthalic acid molecules on rutile TiO2(110)-(1 × 1) surfaces

The structure of terephthalic acid (TPA) molecules adsorbed on rutile TiO2(110)-(1 × 1) has been investigated by scanning tunneling microscopy (STM). Molecularly resolved STM images show formation of monolayer with the tendency of TPA molecules to form dimer rows along the [001] substrate direction. The ability to image functional groups by the STM tip, and single molecule diffusion are demonstrated. The quality and stability of the monolayer are tested, including the resistance against air exposure. On the basis of results obtained, the model of TPA adsorption on the rutile TiO2(110)-(1 × 1) is proposed

Adsorption of organic molecules on the TiO2(011) surface: STM study

High resolution scanning tunneling microscopy has been applied to investigate adsorption and self-assembly of large organic molecules on the TiO(2)(011) surface. The (011) face of the rutile titania has been rarely examined in this context. With respect to possible industrial applications of rutile, quite often in a powder form, knowledge on behavior of organic molecules on that face is required. In the presented study we fill in the gap and report on experiments focused on the self-assembly of organic nanostructures on the TiO(2)(011) surface. We use three different kinds of organic molecules of potential interest in various applications, namely, PTCDA and CuPc representing flat, planar stacking species, and Violet Landers specially designed for new applications in molecular electronics. In order to reach a complete picture of molecular behavior, extended studies with different surface coverage ranging from single molecule up to 2 monolayer (ML) thick films are performed. Our results show that the adsorption behavior is significantly different from previously observed for widely used metallic templates. Creation of highly ordered molecular lines, quasi-ordered wetting layers, controlled geometrical reorientation upon thermal treatment, existence of specific adsorption geometries, and prospects for tip-induced molecule ordering and manipulation provide better understanding and add new phenomena to the knowledge on the (011) face of rutile titania

Adsorption of large organic molecules on clean and hydroxylated rutile TiO2(110) surfaces

Behavior of large organic molecules equipped with spacer groups (Violet Landers, VL) on the TiO(2)(110)-(1x1) surfaces is investigated by means of high-resolution scanning tunneling microscopy (STM). Two distinct adsorption geometries are observed. We demonstrate that the molecule adsorption morphology can be alternated by well-controlled STM tip-induced manipulation. It is used to probe the mobility of molecules and reveals locking in one of the analyzed adsorption sites, thus allow to enhance or reduce the mobility along the [001] direction. Field induced hydrogen desorption is used to perform lateral STM manipulation on a hydroxyl-free surface, which provides insight into the influence of surface hydroxyl groups on the molecule behavior. The ability to image with submolecular resolution both the central board and the spacer groups of the VL molecule is demonstrated

Supramolecular ordering of PTCDA molecules : the key role of dispersion forces in an unusual transition from physisorbed into chemisorbed state

Adsorption and self-assembly of large pi-conjugated 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on rutile TiO2(110) surface have been investigated using a combination of high-resolution scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory calculations with inclusion of Grimme treatment of the dispersion forces (DFT-D). Evolution of the STM images as a function of PTCDA coverage Is owed by transition of the adsorption mode from physisorbed single adspecies and meandering stripes into spontaneously ordered chemisorbed molecular assemblies. This change in the adsorption fashion is accompanied by significant bending of the intrinsically flat, yet elastic, PTCDA molecule, which allows for strong electronic coupling of the dye adspecies with the TiO2 substrate. Extensive DFT-D modeling has revealed that adsorption is controlled by interfacial and intermolecular dispersion forces playing a dominant role in the adsorption of single PTCDA species, their self-organization into the meandering stripes, and at the monolayer coverage acting collectively to surmount the chemisorption energy barrier associated with the molecule bending. Analysis of the resulting density of states has revealed that alignment of the energy levels and strong electronic coupling at the PTCDA/TiO2 interface are beneficial for dye sensitization purpose