Caterina Maria Tone

Hierarchical surface structuring is a critical aspect of advanced materials design, impacting fields ranging from optics to biomimetics. Among several laser-based methods for complex structuring of photo-responsive surfaces, the broadband vectorial interferometry proposed here offers unique performances. Such a method leverages a polychromatic laser source, an unconventional choice for holographic encoding, to achieve deterministic multiscale surface structuring through interference light patterning. Azopolymer films are used as photosensitive substrates. By exploring the interaction between optomechanical stress modulations at different spatial periodicities induced within the polymer bulk, we demonstrate the emergence of hierarchical Fourier surfaces composed of multiple deterministic levels. These structures range from sub-micrometer to tens of micrometers scale, exhibiting a high degree of control over their morphology. The experimental findings reveal that the optical encoding scheme significantly influences the resulting topographies. The polarization light patterns lead to more regular and symmetric hierarchical structures compared to those obtained with intensity patterns, underscoring the role of vectorial light properties in controlling surface morphologies. The proposed method is fully scalable, compatible with more complex recording schemes (including multi-beam interference), and it is applicable to a wide range of advanced technological fields. These include optics and photonics (diffractive elements, polarimetric devices), biomimetic surfaces, topographical design, information encoding, and anti-counterfeiting, offering a rapid, reliable, and versatile strategy for high-precision surface structuring at a submicrometric scale.

This study introduces a novel plasmonic nanocomposite platform, where gold nanoparticles (AuNPs) are synthesized in situ within a polydimethylsiloxane (PDMS) film. The innovative fabrication process leverages ethyl acetate swelling to achieve a uniform distribution of AuNPs, eliminating the need for additional reagents. The resulting nanocomposite film exhibits exceptional photothermal conversion capabilities, efficiently converting absorbed light into heat and rapidly reaching high temperatures. Furthermore, the platform is biofunctionalized with the phosphotriesterase enzyme, not only enabling the degradation of organophosphate pesticides but also showcasing the potential for multifunctional applications. The platform's ability to be regenerated after use underscores its sustainability for repeated applications.

The behavior of lyotropic chromonic liquid crystals (LCLCs) in confined environments is an interesting research field that still awaits exploration, with multiple key variables to be uncovered and understood. Microfluidics is a highly versatile technique that allows us to confine LCLCs in micrometric spheres. As microscale networks offer distinct interplays between the surface effects, geometric confinement, and viscosity parameters, rich and unique interactions emerging at the LCLC-microfluidic channel interfaces are expected. Here, we report on the behavior of pure and chiral doped nematic Sunset Yellow (SSY) chromonic microdroplets produced through a microfluidic flow-focusing device. The continuous production of SSY microdroplets with controllable size gives the possibility to systematically study their topological textures as the function of their diameters. Indeed, doped SSY microdroplets produced via microfluidics, show topologies that are typical of common chiral thermotropic liquid crystals. Furthermore, few droplets exhibit a peculiar texture never observed for chiral chromonic liquid crystals. Finally, the achieved precise control of the produced LCLC microdroplets is a crucial step for technological applications in biosensing and anticounterfeiting.

Induced or spontaneous chirality in natural systems is an intriguing issue. In recent years, a lot of attention has been focused on chirality of chromonic liquid crystals, a class of materials that is able to self-assemble in columnar structures. However, the mechanism involved in the arising of chirality in these materials, that starts at the molecular level and controls the supramolecular structure, is poorly understood; however, it is certainly affected by ionic strength. In this work we present the results obtained doping Cromolyn, a chromonic material, with a strong helical-twisting-power peptide, and confining it in a spherical geometry. We demonstrate, by means of optical polarized microscopy and structural analysis, that both the geometrical constraint and the presence of the chiral dopant enhance the chiral effect; we also demonstrate that they favor the rise of a highly ordered helical superstructure, that may be optimized upon adding an ionic dye to the system. Finally, we report a procedure for the preparation of free-standing polymeric films, embedding and preserving the microspheres, and paving the way for the creation of biocompatible and eco-friendly optical devices to be used in the sensor and anticounterfeiting fields.

Azobenzene‐based light‐responsive thin films are emerging as appealing candidates for smart cell‐culture substrates. Their attraction lies in the fact that they can be reversibly photo‐patterned, providing a route for dynamically mimicking the remodeling of the extracellular matrix. However, since the cells need to be cultured in aqueous environment, a key parameter in the layout of any biological application is the stability of the surface underwater. In this work, the authors perform a detailed investigation on the surface stability of azobenzene‐based thin films in water and in a biologically relevant aqueous medium in which surface blistering occurs, as a result of water–material interaction. The phenomenon arises due to film delamination, and it can be prevented by changing the underlying substrate, by an additional coating layer, or by photo‐induced control over the film permeability. It is also shown that the blister orientation can be controlled with polarized light. Furthermore, a simple model based on osmotic pressure is proposed to explain the blister formation. These findings provide a comprehensive overview of the interaction between water and the photo‐responsive film surface, pertinent for engineering biomaterials with enhanced dynamic control over the cell–material interface.

Mechano-bactericidal materials rely on mechanical interactions between nanomaterials and bacteria, and are promising antimicrobial strategies that overcome bacterial resistance. However, the real effect of mechanical vs chemical action on their activity is under debate. In this paper we quantify the forces necessary to produce critical damage to the bacterial cell wall by performing simultaneous nanoindentation and fluorescence imaging of single bacterial cells. Our experimental setup allows puncturing the cell wall of an immobilized bacterium with the tip of an atomic force microscope (AFM), and following in real-time the increase in fluorescence signal from a cell membrane integrity marker. We correlate the forces exerted by the AFM tip with the fluorescence dynamics for tens of cells, and we find that forces above 20 nN are necessary to exert critical damage. Moreover, a similar experiment is performed in which bacterial viability is assessed through physiological activity, in order to gain a more complete view of the effect of mechanical forces on bacteria. Our results contribute to the quantitative understanding of the interaction between bacteria and nanomaterials.

A combination of time-resolved optical spectroscopy and nanoscale imaging has been used to study the complex binding to amyloids of a photocatalyst that selectively photo-oxygenates pathogenic aggregates, as well as the consequences of its irradiation. Correlative atomic force microscopy (AFM) and fluorescence microscopy reveals topography-dependent binding of the dye to model β-lactoglobulin fibers, which may also explain the observed difference in their response to photodegradation. We provide direct evidence of the photosensitization of singlet oxygen by the photocatalyst bound to amyloid fibers by direct detection of its NIR phosphorescence. The effect of singlet oxygen at the molecular level brings about nanoscale morphological changes that can be observed with AFM at the single-fiber level. We also find differential response of two α-synuclein mutants to photodamage, which can be rationalized by the presence of amino acids susceptible to photo-oxygenation. Overall, our results help to unravel some of the complexity associated to highly heterogeneous amyloid populations, and contribute to the development of improved phototherapeutic strategies for amyloid-related disorders.

Lyotropic chromonic liquid crystals (LCLC) are a kind of LCs far less known and more difficult to control than conventional thermotropic nematics. Nevertheless, LCLCs are a preferred option -often the only one- for applications where hydrophilic materials must be employed. Being water-soluble, LCLC can be used in numerous biology related devices, for example in target detection in lab-on-chip devices. However, their properties and procedures to align them are still less explored, with only a very limited number of options available, especially for homeotropic alignment. In this work, novel organic alignment layers and alignment properties have been explored for selected LCLCs. Non-conventional organic alignment layers were tested and new suitable procedures and materials for both homogeneous and homeotropic alignments have been found. Full Text: PDF ReferencesS.L. Hefinstine, O.D. Lavrentovich, C.J. Woolverton, "Lyotropic liquid crystal as a real-time detector of microbial immune complexes", Lett. Appl. Microbiol. 43, 27 (2006). CrossRef M.A. Geday, M. Ca-o-García, J.M. Escolano, E. Otón, J.M. Otón, X. Quintana, Conference on Liquid Crystals CLC'16, Poland (2016).M.A. Geday, E. Otón, J.M. Escolano, J.M. Otón, X. Quintana, Patent WO 2015193525 (2015). DirectLink Yu.A. Nastishin et al., "Optical characterization of the nematic lyotropic chromonic liquid crystals: Light absorption, birefringence, and scalar order parameter", Phys. Rev. E, 72 (4) 41711 (2005). CrossRef A. Mcguire, et al., "Orthogonal Orientation of Chromonic Liquid Crystals by Rubbed Polyamide Films", Chem. Phys. Chem. 15 (7) (2014). CrossRef J. Jeong, et al., "Homeotropic Alignment of Lyotropic Chromonic Liquid Crystals Using Noncovalent Interactions", Langmuir 30(10) 2914 (2014). CrossRef J.Y. Kim, H.-Tae Jung, "Macroscopic alignment of chromonic liquid crystals using patterned substrates", Phys. Chem. Chem. Phys. 18, 10362 (2016). CrossRef E. Otón, J.M. Escolano, X. Quintana, J.M. Otón, M.A. Geday, "Aligning lyotropic liquid crystals with silicon oxides", Liq. Cryst. 42 (8) 1069 (2015). CrossRef H.S. Park, et al., "Condensation of Self-Assembled Lyotropic Chromonic Liquid Crystal Sunset Yellow in Aqueous Solutions Crowded with Polyethylene Glycol and Doped with Salt", Langmuir 27, 4164 (2011). CrossRef H.S. Park, et al., "Self-Assembly of Lyotropic Chromonic Liquid Crystal Sunset Yellow and Effects of Ionic Additives", J. Phys. Chem. B 112, 16307 (2008). CrossRef R Caputo et al., "POLICRYPS: a liquid crystal composed nano/microstructure with a wide range of optical and electro-optical applications", J. Opt. A: Pure Appl. Opt. 11, 024017 (2009). CrossRef