Fluid-driven bacterial accumulation in proximity of laser-textured surfaces.

In this work we investigated the role of fluid in the initial phase of bacterial adhesion on textured surfaces, focusing onto the approach of the bacterial cells towards the surface. In particular, stainless steel surfaces textured via femtosecond laser interaction have been considered. The method combined a simulation routine, based on the numerical solution of Navier-Stokes equations, and the use of a theoretical model, based on the Smoluchowski's equation. Results highlighted a slowdown of the fluid velocity field in correspondence of the surface dales. In addition, a shear induced accumulation on the top of the surface protrusions was predicted for motile bacterial species, E. coli. In particular, we observed a role of the surface protrusions in increasing the range over which motile bacterial species are attracted towards the surface through a rheotactic mechanism. In other words, we found that, in certain conditions of fluid flow and textured surface morphology, surface protrusions act as a sort of "rheotactic antennas".

WO3 Nanowires Enhance Molecular Alignment and Optical Anisotropy in Electrospun Nanocomposite Fibers: Implications for Hybrid Light-Emitting Systems.

The molecular orientation in polymer fibers is investigated for the purpose of enhancing their optical properties through nanoscale control by nanowires mixed in electrospun solutions. A prototypical system, consisting of a conjugated polymer blended with polyvinylpyrrolidone, mixed with WO3 nanowires, is analyzed. A critical strain rate of the electrospinning jet is determined by theoretical modeling at which point the polymer network undergoes a stretch transition in the fiber direction, resulting in a high molecular orientation that is partially retained after solidification. Nearing a nanowire boundary, local adsorption of the polymer and hydrodynamic drag further enhance the molecular orientation. These theoretical predictions are supported by polarized scanning near-field optical microscopy experiments, where the dichroic ratio of the light transmitted by the fiber provides evidence of increased orientation nearby nanowires. The addition of nanowires to enhance molecular alignment in polymer fibers might consequently enhance properties such as photoluminescence quantum yield, polarized emission, and tailored energy migration, exploitable in light-emitting photonic and optoelectronic devices and for sensing applications.

Towards Laser-Textured Antibacterial Surfaces.

Escherichia coli and Staphylococcus aureus bacterial retention on mirror-polished and ultrashort pulse laser-textured surfaces is quantified with a new approach based on ISO standards for measurement of antibacterial performance. It is shown that both wettability and surface morphology influence antibacterial behavior, with neither superhydrophobicity nor low surface roughness alone sufficient for reducing initial retention of either tested cell type. Surface structures comprising spikes, laser-induced periodic surface structures (LIPSS) and nano-pillars are produced with 1030 nm wavelength 350 fs laser pulses of energy 19.1 µJ, 1.01 µJ and 1.46 µJ, respectively. SEM analysis, optical profilometry, shear force microscopy and wettability analysis reveal surface structures with peak separations of 20-40 µm, 0.5-0.9 µm and 0.8-1.3 µm, average areal surface roughness of 8.6 µm, 90 nm and 60 nm and static water contact angles of 160°, 119° and 140°, respectively. E. coli retention is highest for mirror-polished specimens and spikes whose characteristic dimensions are much larger than the cell size. S. aureus retention is instead found to be inhibited under the same conditions due to low surface roughness for mirror-polished samples (Sa: 30 nm) and low wettability for spikes. LIPSS and nano-pillars are found to reduce E. coli retention by 99.8% and 99.2%, respectively, and S. aureus retention by 84.7% and 79.9% in terms of viable colony forming units after two hours of immersion in bacterial broth due to both low wettability and fine surface features that limit the number of available attachment points. The ability to tailor both wettability and surface morphology via ultrashort pulsed laser processing confirms this approach as an important tool for producing the next generation of antibacterial surfaces.

Near-field surface plasmon field enhancement induced by rippled surfaces.

The occurrence of plasmon resonances on metallic nanometer-scale structures is an intrinsically nanoscale phenomenon, given that the two resonance conditions (i.e., negative dielectric permittivity and large free-space wavelength in comparison with system dimensions) are realized at the same time on the nanoscale. Resonances on surface metallic nanostructures are often experimentally found by probing the structures under investigation with radiation of various frequencies following a trial-and-error method. A general technique for the tuning of these resonances is highly desirable. In this paper we address the issue of the role of local surface patterns in the tuning of these resonances as a function of wavelength and electric field polarization. The effect of nanoscale roughness on the surface plasmon polaritons of randomly patterned gold films is numerically investigated. The field enhancement and relation to specific roughness patterns is analyzed, producing many different realizations of rippled surfaces. We demonstrate that irregular patterns act as metal-dielectric-metal local nanogaps (cavities) for the resonant plasmonic field. In turn, the numerical results are compared to experimental data obtained via aperture scanning near-field optical microscopy.

Linear and circular dichroism in porphyrin J-aggregates probed by polarization modulated scanning near-field optical microscopy.

Polarization modulated scanning near-field optical microscopy (PM-SNOM) is effective in detecting circular and linear dichroism with sub-wavelength resolution. PM-SNOM investigation of the chiroptical properties of single ribbon-like nanosized J-aggregates formed by acid induced aggregation of tris-(4-sulfonatophenyl)phenylporphyrin is reported. Linear dichroism maps give evidence of well-organized chromophores packed in linear arrays within the structure of the nanoribbons. Circular dichroism maps indicate that the molecules forming the nanoribbon have an inherently chiral structure at the local scale.

Conformational Evolution of Elongated Polymer Solutions Tailors the Polarization of Light-Emission from Organic Nanofibers.

Polymer fibers are currently exploited in tremendously important technologies. Their innovative properties are mainly determined by the behavior of the polymer macromolecules under the elongation induced by external mechanical or electrostatic forces, characterizing the fiber drawing process. Although enhanced physical properties were observed in polymer fibers produced under strong stretching conditions, studies of the process-induced nanoscale organization of the polymer molecules are not available, and most of fiber properties are still obtained on an empirical basis. Here we reveal the orientational properties of semiflexible polymers in electrospun nanofibers, which allow the polarization properties of active fibers to be finely controlled. Modeling and simulations of the conformational evolution of the polymer chains during electrostatic elongation of semidilute solutions demonstrate that the molecules stretch almost fully within less than 1 mm from jet start, increasing polymer axial orientation at the jet center. The nanoscale mapping of the local dichroism of individual fibers by polarized near-field optical microscopy unveils for the first time the presence of an internal spatial variation of the molecular order, namely the presence of a core with axially aligned molecules and a sheath with almost radially oriented molecules. These results allow important and specific fiber properties to be manipulated and tailored, as here demonstrated for the polarization of emitted light.

Local mechanical properties of electrospun fibers correlate to their internal nanostructure.

The properties of polymeric nanofibers can be tailored and enhanced by properly managing the structure of the polymer molecules at the nanoscale. Although electrospun polymer fibers are increasingly exploited in many technological applications, their internal nanostructure, determining their improved physical properties, is still poorly investigated and understood. Here, we unravel the internal structure of electrospun functional nanofibers made by prototype conjugated polymers. The unique features of near-field optical measurements are exploited to investigate the nanoscale spatial variation of the polymer density, evidencing the presence of a dense internal core embedded in a less dense polymeric shell. Interestingly, nanoscale mapping the fiber Young's modulus demonstrates that the dense core is stiffer than the polymeric, less dense shell. These findings are rationalized by developing a theoretical model and simulations of the polymer molecular structural evolution during the electrospinning process. This model predicts that the stretching of the polymer network induces a contraction of the network toward the jet center with a local increase of the polymer density, as observed in the solid structure. The found complex internal structure opens an interesting perspective for improving and tailoring the molecular morphology and multifunctional electronic and optical properties of polymer fibers.

Size effects in nanoindentation of hard and soft surfaces.

Nanoindentation experiments carried out with atomic force microscopes (AFMs) open the way to understand size-related mechanical effects that are not present at the macro- or micro-scale. Several issues, currently the subject of a wide and open debate, must be carefully considered in order to measure quantities and retrieve trends genuinely associated with the material behaviour. The shape of the nanoindenter (the AFM tip) is crucial for a correct data analysis; we have recently developed a simple geometrical model to properly describe the tip effect in the nanoindentation process. Here, we demonstrate that this model is valid in indentation of both soft and hard, or relatively hard, materials carried out by two distinct, commercially available, AFM probes. Moreover, we implement the model with a data interpretation approach aimed at preventing underestimation of the tip penetration into the material. Experiments on soft polymeric materials (poly(methyl methacrylate) and polystyrene) and hard or relatively hard (Si, Au, Al) materials are reported. The results demonstrate that true hardness data can be attained also in shallow indentations and that the appearance of size effects strongly depends on data interpretation issues. In addition, we report on stiffness data measured on the considered materials during their nanoindentation.

An atomic force microscopy tip model for investigating the mechanical properties of materials at the nanoscale.

Investigation of the mechanical properties of materials at the nanoscale is often performed by atomic force microscopy nanoindentation. However, substrates with large surface roughness and heterogeneity demand careful data analysis. This requirement is even more stringent when surface indentations with a typical depth of a few nanometers are produced to test material hardness. Accordingly, we developed a geometrical model of the nanoindenter, which was first validated by measurements on a reference gold sample. Then we used this technique to investigate the mechanical properties of a coating layer made of Balinit C, a commercially available alloy with superior anti-wear features deposited on steel. The reported results support the feasibility of reliable hardness measurements with truly nanosized indents.