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Bioinspired nanoparticles have recently been gaining attention as promising multifunctional nanoplatforms for therapeutic applications in cancer, including breast cancer. Here, the efficiency of the chemo-photothermal and photoacoustic properties of hybrid albumin-modified nanoparticles (HSA-NPs) loaded with doxorubicin was evaluated in a three-dimensional breast cancer cell model. The HSA-NPs showed a higher uptake and deeper penetration into breast cancer spheroids than healthy breast cell 3D cultures. Confocal microscopy revealed that, in tumour spheroids incubated with doxorubicin-loaded NPs for 16 h, doxorubicin was mainly localised in the cytoplasm, while a strong signal was detectable at the nuclear level after 24 h, suggesting a time-dependent uptake. To evaluate the cytotoxicity of doxorubicin-loaded NPs, tumour spheroids were treated for up to 96 h with increasing concentrations of NPs, showing marked toxicity only at the highest concentration of doxorubicin. When doxorubicin administration was combined with laser photothermal irradiation, enhanced cytotoxicity was observed at lower concentrations and incubation times. Finally, the photoacoustic properties of doxorubicin-loaded NPs were evaluated in tumour spheroids, showing a detectable signal increasing with NP concentration. Overall, our data show that the combined effect of chemo-photothermal therapy results in a shorter exposure time to doxorubicin and a lower drug dose. Furthermore, owing to the photoacoustic properties of the NPs, this nanoplatform may represent a good candidate for theranostic applications.

Photoacoustics (PA) is gaining increasing credit among biomolecular imaging methodologies by virtue of its poor invasiveness, deep penetration, high spatial resolution, and excellent endogenous contrast, without the use of any ionizing radiation. Recently, we disclosed the excellent PA response of a self-structured biocompatible nanoprobe, consisting of ternary hybrid nanoparticles with a silver core and a melanin component embedded into a silica matrix. Although preliminary evidence suggested a crucial role of the Ag sonophore and the melanin-containing nanoenvironment, whether and in what manner the PA response is controlled and affected by the self-structured hybrid nanosystems remained unclear. Because of their potential as multifunctional platforms for biomedical applications, a detailed investigation of the metal-polymer-matrix interplay underlying the PA response was undertaken to understand the physical and chemical factors determining the enhanced response and to optimize the architecture, composition, and performance of the nanoparticles for efficient imaging applications. Herein, we provide the evidence for a strong synergistic interaction between eumelanin and Ag which suggests an important role in the in situ-generated metal-organic interface. In particular, we show that a strict ratio between melanin and silver precursors and an accurate choice of metal nanoparticle dimension and the kind of metal are essential for achieving strong enhancements of the PA response. Systematic variation of the metal/melanin component is thus shown to offer the means of tuning the stability and intensity of the photoacoustic response for various biomedical and theranostic applications.

Hybrid nanomaterials have attracted research interest owing to their intriguing properties, which may offer new diagnostic options with triggering features, able to realize a new kind of tunable nanotherapeutics. Hybrid silica/melanin nanoparticles (NPs) containing silver seeds (Me-laSil_Ag-HSA NPs) disclosed relevant photoacoustic contrast for molecular imaging. In this study we explored therapeutic function in the same nanoplatform. For this purpose, MelaSil_Ag-HSA were loaded with doxorubicin (DOX) (MelaSil_Ag-HSA@DOX) and tested to assess the efficiency of drug delivery combined with concurrent photothermal treatment. The excellent photothermal properties allowed enhanced cytotoxic activity at significantly lower doses than neat chemotherapeutic treatment. The results revealed that MelaSil_Ag-HSA@DOX is a promising platform for an integrated photothermal (PT) chemotherapy approach, reducing the efficacy concentration of the DOX and, thus, potentially limiting the several adverse side effects of the drug in in vivo treatments.

Hybrid Melanin-TiO 2 nanoparticles are promising bioinspired antibacterial agents for biomedical coatings and food-packaging fields. However, due to a very low colloidal stability, they showed a high tendency to self-aggregate and rapidly precipitate, making not easy their use in aqueous medium to produce homogeneous antimicrobial coatings or nanocomposites. A valid strategy to improve their dispersion is the combination with a hydrophilic water-soluble polymer such as poly-vinyl-alcohol (PVA), which is a good choice to improve the colloidal stability of nanoparticles and to modulate their agglomeration. In this work, we propose an in-situ synthetic approach based on the hydrothermal route, by which the hybrid Melanin-TiO 2 nanoparticles were prepared starting from the inorganic and organic precursors in the presence of PVA. Combined approach of TEM, XRD, TG/DSC, EPR and DLS techniques allows for assessing the PVA role in the formation of hybrids and on their morphological features as well as colloidal stability and aqueous dispersion. Antibacterial tests demonstrated the biocide activity of PVA/Melanin-TiO 2 nanoparticles against Escherichia coli bacterial cultures, which resulted partially influenced by the PVA content. This study provides key information on the mutual influence of organic/inorganic components on the functional properties of the final hybrid nanocomposites, contributing to define a much more far-reaching implementation in the synthesis of bioinspired polymer-based nanocomposites., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Developing advanced materials for wound dressings is a very challenging, yet unaddressed task. These systems are supposed to act as temporary skin substitutes, performing multiple functions, including fluid absorption and antimicrobial action, supporting cell proliferation and migration in order to promote the skin regeneration process. Following a global bioinspired approach, in this study, we developed a multifunctional textile for wound dressing applications. Biodegradable polyhydroxybutyrate/poly-3-caprolactone (PHB/PCL) mats were fabricated by electrospinning to mimic the extracellular matrix (ECM), thus providing structural and biochemical support to tissue regeneration. Furthermore, inspired by nature's strategy which exploits melanin as an effective weapon against pathogens infection, PHB/PCL mats were modified with hybrid Melanin-TiO 2 nanostructures. These were combined to PHB/PCL mats following two different strategies: in-situ incorporation during electrospinning process, alternately ex-post coating by electrospraying onto obtained mats. All samples revealed huge water uptake and poor cytotoxicity towards HaCat eukaryotic cells. Melanin-TiO 2 coating conferred PHB/PCL mats significant antimicrobial activity towards both Gram(+) and Gram(-) strains, marked hydrophilic properties as well as bioactivity which is expected to promote materials-cells interaction. This study is going to provide a novel paradigm for the design of active wound dressings for regenerative medicine., (Copyright © 2021 Elsevier B.V. All rights reserved.)

We disclose herein the first example of stable monodispersed hybrid nanoparticles (termed MelaSil-NPs) made up of eumelanin biopolymer intimately integrated into a silica nanoscaffold matrix and endowed with high antioxidant and cytoprotective effects associated with a specific subcellular localization. MelaSil-NPs have been fabricated by an optimized sol-gel methodology involving ammonia-induced oxidative polymerization of a covalent conjugate of the eumelanin building block 5,6-dihydroxyindole-2-carboxylic acid (DHICA) with 3-aminopropyltriethoxysilanes (APTS). They displayed a round-shaped (ca. 50-80 nm) morphology, exhibited the typical electron paramagnetic resonance signal of eumelanin biopolymers, and proved effective in promoting decomposition of hydrogen peroxide under physiologically relevant conditions. When administered to human ovarian cancer cells (A2780) or cervical cancer cells (HeLa), MelaSil-NPs were rapidly internalized and colocalized with lysosomes and exerted efficient protecting effects against hydrogen peroxide-induced oxidative stress and cytotoxicity.

A large number of recent literature data focus on modification/modulation of surface chemistry of inorganic materials in order to improve their functional properties. Melanins, a wide class of natural pigments, are recently emerging as a powerful organic component for developing bioinspired active material for a large number of applications from organoelectronics to bioactive compounds. Here we report the use of the approach referred as "chimie douce", involving in situ formation of the hybrids through reactions of precursors under mild conditions, to prepare novel hybrid functional architectures based on eumelanin like 5,6 dihydroxyindole-2-carboxylic acid (DHICA) polymer and TiO2. Two synthesis procedures were carried out to get DHICA-melanin coated TiO2 nanoparticles as well as mixed DHICA/TiO2 hybrid nanostructures. Such systems were characterized through EPR, FT-IR and fluorescence spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and TEM microscopy in order to assess the effect of synthesis path as well as of DHICA content on structural, morphological and optical properties of TiO2 nanostructures. In particular, EPR, FT-IR spectra and TGA analysis confirmed the presence of DHICA-melanin in these samples. TEM measurements indicated the formation of the nanoparticles having relatively narrow size distribution with average particle size of about 10nm. DHICA-melanin does act as a morphological agent affecting morphology of hybrid nanostructures. XRD analysis proved that TiO2 hybrid nanoparticles kept anatase structures for DHICA-melanin contents within the range of investigated compositions, i.e. up to 50% wt/wt., (Copyright © 2012 Elsevier B.V. All rights reserved.)

PEGylated silica nanoparticles, giving very stable aqueous sols, were successfully functionalised with rhodamine, one of the more stable fluorophore; they were also decorated with the targeting agent folic acid (FA) and charged with the well known drug doxorubicin. Rhodamine functionalization required a modification of the synthesis route of the nanoparticles (NP). Functionalization with FA required activation with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride. Folate decorated NP were easily charged with doxorubicin. The experimental results proved the successfulness of the functionalization. The bond to the NP does not reduce the therapeutic efficacy of the drug. The calculated encapsulation efficiency (32 %) was only a little lower than the value (47 %) reported for the very popular PEGylated PLGA NP.

A hybrid of poly(2-hydroxyethylmethacrylate) (pHEMA), a polymer widely employed for biomedical applications, and silica gel, exhibiting a well-known bioactivity, was produced by sol-gel. The amount of the inorganic precursor, tetraethoxysilane (TEOS), was mixed to the organic monomer, so as to have a final concentration of 30% (w/w) of silica gel to the mass of polymer. The nanocomposite was characterized for its composition by thermogravimetric (TG) analysis, swelling behavior, glass transition temperature using differential thermal analysis (DTA), morphology through scanning electron microscopy (SEM), and bioactivity using FT-IR spectroscopy, SEM, and energy dispersive system (EDS). The nanocomposite showed phase separation between the polymer and the silica gel, improved thermal stability and swelling properties and higher glass transition temperature than pHEMA. Moreover, bioactive SiO(2) gel nanoparticles promoted apatite formation on the surface of the modified hydrogel, when it was soaked in SBF. Therefore, the obtained bioactive nanocomposite can be used to make bioactive scaffold for bone engineering., (2007 Wiley Periodicals, Inc.)

ABSTRACT In this work, experimental results about poly(butylene terephthalate) (PBT) based nanocomposites filled with various amounts of silica nanoparticles (NPs) are reported. Two different types of filler are used: silica gel NPs, produced through the Stöber method, and a commercial fumed silica, both coated by a PBT shell. Melt-mixed samples have been thoroughly investigated by scanning and transmission electron microscopy, infrared Fourier transform spectroscopy (FTIR), thermal gravimetric analysis, differential scanning calorimetry, wide and small angle X-ray diffraction, and dynamic mechanical analysis. A fine and very good dispersion of NPs into the polymeric matrix is revealed through the morphological analysis when Stöber NPs were used as filler with respect to systems including commercial fumed silica particles. This evidence, combined with matrix-filler interactions revealed by FTIR spectroscopy, justifies the enhancement of both storage modulus and glass transition temperature of the former samples in comparison with reference pristine PBT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46006. [ABSTRACT FROM AUTHOR]

Abstract: Submicrometric particles were obtained, through the Stöber method, from alcoholic (ethanol) solutions of tetraethoxysilane (TEOS) and 3-aminopropyl-triethoxysilane (APTS), at total alcoxide concentration 0.15M, in the presence of ammonia (0.1M) and water (8.8M) and fluorescein sodium (0.40mM). Nano-sized particles were obtained from solutions 0.15M of TEOS or APTS. A surprising particle size increase was observed when mixing TEOS and APTS at constant overall alkoxide content (0.15M). The result was explained, on the basis of the known aggregation model, by taking into account that the substitution of TEOS to APTS and vice-versa changes the ratio of nucleation and aggregation rates and that nuclei of different size are expected to form when the alkoxides are mixed. The mixing appears to change the evolution of particle population favouring the establishment of a size distribution wherein the dominant aggregation event can be between the freshly generated nuclei and large aggregates, which is the faster aggregation event. The closer is the TEOS/APTS ratio to 1 the sooner particles size differentiation would occur and the fewer but greater particles would form, in short times. [Copyright &y& Elsevier]