"Pop goes the particle". Here we report on the preparation of redox responsive mesoporous organo-silica nanoparticles containing disulfide (S-S) bridges (ss-NPs) that, even upon the exohedral grafting of targeting ligands, retained their ability to undergo structural degradation, and increase their local release activity when exposed to a reducing agent. This degradation could be observed also inside glioma C6 cancer cells. Moreover, when anticancer drug-loaded pristine and derivatized ss-NPs were fed to glioma C6 cells, the responsive hybrids were more effective in their cytotoxic action compared to non-breakable particles. The possibility of tailoring the surface functionalization of this hybrid, yet preserving its self-destructive behavior and enhanced drug delivery properties, paves the way for the development of effective biodegradable materials for in vivo targeted drug delivery.

The direct delivery of specific proteins to live cells promises a tremendous impact for biological and medical applications, from therapeutics to genetic engineering. However, the process mostly involves tedious techniques and often requires extensive alteration of the protein itself. Herein we report a straightforward approach to encapsulate native proteins by using breakable organosilica matrices that disintegrate upon exposure to a chemical stimulus. The biomolecule-containing capsules were tested for the intracellular delivery of highly cytotoxic proteins into C6 glioma cells. We demonstrate that the shell is broken, the release of the active proteins occurs, and therefore our hybrid architecture is a promising strategy to deliver fragile biomacromolecules into living organisms.

Multifunctional materials can be engineered by combining multiple chemical components, each conferring a well-defined function to the ensemble. Graphene is at the centre of an ever-growing research effort due to its combination of unique properties. Here we show that the large conformational change associated with the trans–cis photochemical isomerization of alkyl-substituted azobenzenes can be used to improve the efficiency of liquid-phase exfoliation of graphite, with the photochromic molecules acting as dispersion-stabilizing agents. We also demonstrate reversible photo-modulated current in two-terminal devices based on graphene–azobenzene composites. We assign this tuneable electrical characteristics to the intercalation of the azobenzene between adjacent graphene layers and the resulting increase in the interlayer distance on (photo)switching from the linear trans-form to the bulky cis-form of the photochromes. These findings pave the way to the development of new optically controlled memories for light-assisted programming and high-sensitive photosensors.

A Pt(II) complex, bearing an oligo-ethyleneoxide pendant, is able to selfassemble in ultralong ribbons that display mechanochromism upon nanoscale mechanical stimuli, delivered through atomic force microscopy (AFM). Such observation paves the way to fine understanding and manipulation of the mechanochromic properties of such material at the nanoscale. AFM allows quantitative assessment of nanoscale mechanochromism as arising from static pressure (piezochromism) and from shear-based mechanical stimuli (tribochromism), and to compare them with bulk pressure-dependent luminescence observed with diamond-anvil cell (DAC) technique. Confocal spectral imaging reveals that mechanochromism only takes place within short distance from the localized mechanical stimulation, which allows to design high-density information writing with AFM nanolithography applied on individual self-assembled ribbons. Each ribbon hence serves as an individual microsystem for data storage. The orange luminescence of written information displays high contrast compared to cyan native luminescence; moreover, it can be selectively excited with visible light. In addition, ribbons show photochromism, i.e., the emission spectrum changes upon exposure to light, in a similar way as upon mechanical stress. Photochromism is here conveniently used to conceal and eventually erase information previously written with nanolithography by irradiation.

Mesoporous silica nanoparticles (MSNPs), 100 nm in size, incorporating a Cy5 fluorophore within the silica framework, are synthesized and loaded with the anti-cancer drug temozolomide (TMZ), used in the treatment of gliomas. The surface of the particles is then decorated, using electrostatic interactions, with a polyarginine-peptide nucleic acid (R8-PNA) conjugate targeting the miR221 microRNA. The multi-functional nanosystem thus obtained is rapidly internalized into glioma C6 or T98G cells. The anti-miR activity of the PNA is retained, as confirmed by reverse transcription polymerase chain reaction (RT-PCR) measurements and induction of apoptosis is observed in temozolomide-resistant cell lines. The TMZ-loaded MSNPs show an enhanced pro-apoptotic effect, and the combined effect of TMZ and R8-PNA in the MSNPs shows the most effective induction of apoptosis (70.9% of apoptotic cells) thus far achieved in the temozolomide-resistant T98G cell line.

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The challenge of mimicking the extracellular matrix with artificial scaffolds that are able to reduce immunoresponse is still unmet. Recent findings have shown that mesenchymal stem cells (MSC) infiltrating into the implanted scaffold have effects on the implant integration by improving the healing process. Toward this aim, a novel polyamidoamine-based nanocomposite hydrogel is synthesized, cross-linked with porous nanomaterials (i.e., mesoporous silica nanoparticles), able to release chemokine proteins. A comprehensive viscoelasticity study confirms that the hydrogel provides optimal structural support for MSC infiltration and proliferation. The efficiency of this hydrogel, containing the chemoattractant stromal cell-derived factor 1α (SDF-1α), in promoting MSC migration in vitro is demonstrated. Finally, subcutaneous implantation of SDF-1α-releasing hydrogels in mice results in a modulation of the inflammatory reaction. Overall, the proposed SDF-1α-nanocomposite hydrogel proves to have potential for applications in tissue engineering.

One of the major problems related to the use of dyes in industrial applications is their elimination from the water or soil and eventually their recovery and reutilization. In this context, a new biocompatible material, previously considered suitable for biomedical applications, is presented for the first time, as an innovative adsorbent material for wastewater treatment. A polyamidoamine‐based hydrogel, prepared by Michael‐type polyaddition in water, is used for efficiently adsorbing two anionic toxic textile dyes from aqueous solutions. Several parameters affecting the adsorption process, such as the pH of solutions containing dyes, the amount of hydrogel and dyes, and the effect of temperature, are investigated. Moreover, the hydrogel dehydration and swollen conditions by using dye water solution are studied by Thermo‐Gravimetry (TG) and Differential Scanning Calorimetry (DSC) analyses, finding that the dehydration temperature plays a relevant role in determining the subsequent adsorbing behavior. The material characterization shows that the adsorption process can be attributed to a combination of electrostatic attraction and intermolecular interactions between hydrogel functional groups and the dye molecules. Visible absorption spectroscopy and Fourier Transform InfraRed‐Attenuated Total Reflectance (FTIR‐ATR) support the findings. The kinetics of the dye adsorption process are also evaluated, together with the adsorption isotherms.