Many cellular phenomena occur on the biomembranes. There are plenty of molecules (natural or xenobiotics) that interact directly or partially with the cell membrane. Biomolecules, such as several peptides (e.g., antimicrobial peptides) and proteins, exert their effects at the cell membrane level. This feature makes necessary investigating their interactions with lipids to clarify their mechanisms of action and side effects necessary. The determination of molecular lipid/water partition constants (K _p ) is frequently used to quantify the extension of the interaction. The determination of this parameter has been achieved by using different methodologies, such as UV-Vis absorption spectrophotometry, fluorescence spectroscopy and ζ-potential measurements. In this work, we derived and tested a mathematical model to determine the K _p from ζ-potential data. The values obtained with this method were compared with those obtained by fluorescence spectroscopy, which is a regular technique used to quantify the interaction of intrinsically fluorescent peptides with selected biomembrane model systems. Two antimicrobial peptides (BP100 and pepR) were evaluated by this new method. The results obtained by this new methodology show that ζ-potential is a powerful technique to quantify peptide/lipid interactions of a wide variety of charged molecules, overcoming some of the limitations inherent to other techniques, such as the need for fluorescent labeling.

In addition to its traditional application in white pigments, nanocrystalline titania (TiO₂) has optoelectronic and photocatalytic properties (strongly dependent on crystallinity, particle size, and surface structure) that grant this naturally occurring oxide new technological applications. Sol-gel is one of the most widely used methods to synthesize TiO₂ films and NPs, but the products obtained (mostly oxy-hydrated amorphous phases) require severe heat-treatments to promote crystallization, in which control over size and shape is difficult to achieve. In this work, we obtained new photocatalytic materials based on amorphous titania and measured their electronic band gap. Two case studies are reported that show the enormous potential of amorphous titania as bactericide or photocatalyst. In the first, amorphous sol-gel TiO₂ thin films doped with N (TiO_2−xN_x, x = 0.75) were designed to exhibit a photonic band gap in the visible region. The identification of Ti-O-N and N-Ti-O bindings was achieved by XPS. The photonic band gaps were found to be 3.18 eV for a-TiO₂ and 2.99 eV for N-doped a-TiO₂. In the second study, amorphous titania and amine-functionalized amorphous titania nanoparticles were synthetized using a novel base-catalysed sol-gel methodology. All the synthesized amorphous TiO₂ nanoparticles exhibit bactericide performance (E. coli, ASTME 2149-13).

Conventional therapies to treat cancer often exhibit low specificity, reducing the efficiency of the treatment and promoting strong side effects. To overcome these drawbacks, new ways to fight cancer cells have been developed so far focusing on nanosystems. Different action mechanisms to fight cancer cells have been explored using nanomaterials, being their remote activation one of the most promising. Photo- and sonodynamic therapies are relatively new approaches that emerged following this idea. These therapies are based on the ability of specific agents to generate highly cytotoxic reactive oxygen species (ROS) by external stimulation with light or ultrasounds (US), respectively. Crystalline (TiO₂) and amorphous titania (a-TiO₂) nanoparticles (NPs) present a set of very interesting characteristics, such as their photo-reactivity, photo stability, and effective bactericidal properties. Their production is inexpensive and easily scalable; they are reusable and demonstrated already to be nontoxic. Therefore, these NPs have been increasingly studied as promising photo- or sonosensitizers to be applied in photodynamic/sonodynamic therapies in the future. However, they suffer from poor colloidal stability in aqueous and biological relevant media. Therefore, various organic and polymer-based coatings have been proposed. In this work, the role of a-TiO₂ based NPs synthesized through a novel, room-temperature, base-catalyzed, sol-gel protocol in the generation of ROS and as an enhancer of acoustic inertial cavitation was evaluated under ultrasound irradiation. A novel biomimetic coating based on double lipidic bilayer, self-assembled on the a-TiO₂-propylamine NPs, is proposed to better stabilize them in water media. The obtained results show that the biomimetic a-TiO₂-propylamine NPs are promising candidates to be US responding agents, since an improvement of the cavitation effect occurs in presence of the developed NPs. Further studies will show their efficacy against cancer cells.

Superparamagnetic iron oxide nanoparticles (SPIONs) have shown great potential in biomedicine due to their high intrinsic magnetization behaviour. These are small particles of magnetite or maghemite, and when coated, their surface oxidation is prevented, their aggregation tendency is reduced, their dispersity is improved, and the stability and blood circulation time are increased, which are mandatory requirements in biomedical applications. In this work, SPIONs were synthesized in air through a reduction-precipitation method and coated with four different polymers (Polyethylene glycol(PEG) 1000/6000 and dextran T10/T70). All the synthesized samples were structurally and magnetically characterized by transmission electron microscopy, Fourier transform infra-red spectroscopy, X-ray powder diffraction, Mössbauer spectroscopy, and Superconducting Quantum Interference Device (SQUID) magnetometry. SPIONs centrifuged and dried in vacuum with an average diameter of at least 7.5 nm and a composition ≤60% of maghemite and ≥40% of magnetite showed the best magnetization results, namely a saturation magnetization of ~64 emu/g at 300 K, similar to the best reported values for SPIONs prepared in controlled atmosphere. As far as SPIONs’ coatings are concerned, during their preparation procedure, surface polymers must be introduced after the SPIONs’ precipitation. Furthermore, polymers with shorter chains do not affect the SPIONs’ magnetization performance, although longer chain polymers significantly decrease the coated particle magnetization values, which is undesirable.

Nanomedicine is an emerging treatment approach for many cancers, characterized by having high sensitivity and selectivity for tumor cells and minimal toxic effects induced by the conventional chemotherapeutics. In these context, smart nanoparticles (NPs) are getting increasingly relevant in the development of new therapies. NPs with specific chemical composition and/or structure and being stimuli-responsive to magnetic, light or ultrasound waves are new promising tools. In the present work, amorphous-titania propyl-amine functionalized (a-TiO₂-NH₂) NPs, coated with bovine serum albumin (BSA), are stimulated with high energy shock waves to induce cytotoxic effects in cancer cells. First, a new method to coat a-TiO₂-NH₂ NPs with BSA (a-TiO₂-NH₂/BSA) was proposed, allowing for a high dispersion and colloidal stability in a cell culture media. The a-TiO₂-NH₂/BSA NPs showed no cancer cell cytotoxicity. In a second step, the use of shock waves to stimulate a-TiO₂-NH₂/BSA NPs, was evaluated and optimized. A systematic study was performed in in vitro cell culture aiming to impair the cancer cell viability: NP concentrations, time steps and single versus multiple shock waves treatments were studied. The obtained results highlighted the relevance of NPs design and administration time point with respect to the shock wave treatment and allow to hypothesize mechanical damages to cells.