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The synthesis of nanosized metal–organic frameworks (NMOFs) is requisite for their application as injectable drug delivery systems (DDSs) and other biorelevant purposes. Herein, we have critically examined the role of different synthetic parameters leading to the production of UiO-66 crystals smaller than 100 nm. Of note, we demonstrate the co-modulator role conferred by halide ions, not only to produce NMOFs with precise morphology and size, but also to significantly improve the reaction yield. The resulting NMOFs are highly crystalline and exhibit sustained colloidal stability in different biologically relevant media. As a proof of concept, these NMOFs were loaded with Rhodamine 6G (R6G), which remained trapped in most common biologically relevant media. When incubated with living mammalian cells, the R6G-loaded NMOFs were efficiently internalized and did not impair cell viability even at relatively high doses. The authors acknowledge the financial support of the MCIN/AEI (PID2019-108624RB-I00, RYC-2017-23457, RYC-2019-028238-I), the Xunta de Galicia (ED431F 2017/02, ED431F 2020/11, 2021-CP090, Centro Singular de Investigación de Galicia Accreditation 2019–2022, ED431G 2019/03), the European Union (European RegionalDevelopment Fund – ERDF; H2020-MSCA-ITN grant agreement no. 860942; H2020-FET-Open grant agreement no. 899612; H2020-ICT grant agreement no. 10101694 and INTERREG V-A Spain–Portugal, project 0624_2IQBIONEURO_6_E), and the European Research Council (starting grant no. 950421). M.C.-M. thanks the AEI (FPU19/03155). The authors are grateful for the use of RIAIDT-USC analytical facilities. SI

The study of chromogenic materials and systems is particularly promising for innovative, transparent building envelopes, with thermo-optical properties adaptable to surrounding environmental conditions. This work spots light on the multiple effects of photochromic glazing on the energy consumption of buildings and on the impact that such technologies would have on the visual comfort of occupants. To our knowledge, this is the first work dealing with building integration of spirooxazine-based photochromic films. This experimental and theoretical work aims helping to fill this gap by reporting the results of a study concerning the spirooxazine photochromic molecules, integrated in transparent matrices of polymethylmethacrylate. This work discloses the potential of specific photochromic materials, especially as a function of spectral peculiarities. The figures of merit of this technology have been studied by assuming its integration in an ideal multi-storey office building, and by studying the effects in terms of energy consumption and visual comfort and proposing a comparison with several static commercial glazing technologies. The photochromic glazing demonstrated to offer significant reduction of energy use for cooling, compared to a clear glass (with yearly saving of 4079 kWh, on the Southern facade), and for artificial lighting (with a saving of 3711 kWh), if compared to the commercial solar control glazing. Furthermore, the dynamic behaviour of the photochromic glazing represented the best choice in terms of visual comfort.

Semiconductor nanomaterials are often proposed as photocatalysts for wastewater treatment; silica nanomaterials are still largely unexploited because their photocatalytic performances need improvements, especially under visible light. The present study is a proof-of-concept that amorphous silica colloids once submitted to the proper surface modifications change into an efficient photocatalyst even under low-energy illumination source. For this reason, silica-based colloidal nanomaterials, such as bare (SiO2 NPs), aminated (NH2-SiO2 NPs), and Ag NPs-decorated (Ag-SiO2 NPs) silica, are tested as photocatalysts for the degradation of 9-anthracenecarboxylic acid (9ACA), taken as a model aromatic compound. Interestingly, upon irradiation at 313 nm, NH2-SiO2 NPs induce 9ACA degradation, and the effect is even improved when Ag-SiO2 NPs are used. On the other hand, irradiation at 405 nm activates the plasmon of Ag-SiO2 NPs photocatalyst, providing a faster and more efficient photodegradation. The photodegradation experiments are also performed under white light illumination, employing a low-intensity fluorescent lamp, confirming satisfying efficiencies. The catalytic effect of SiO2-based nanoparticles is thought to originate from photo-excitable surface defects and Ag NP plasmons since the catalytic degradation takes place only when the 9ACA is adsorbed on the surface. In addition, the involvement of reactive oxygen species was demonstrated through a scavenger use, obtaining a yield of 17%. In conclusion, this work shows the applicability of silica-based nanoparticles as photocatalysts through the involvement of silica surface defects, confirming that the silica colloids can act as photocatalysts under irradiation with monochromatic and white light. Graphic abstract Silica and Ag-decorated silica colloids photosensitize the formation of Reactive Oxygen Species with 17% efficiencies. ROS are able to oxidase aromatic pollutants chemi-adsorbed on the surface of the colloids. Silica-silver nanocomposites present a photocatalytic activity useful to degrade aromatic compounds.

The prospect of tuning the energy of emitting states through external stimuli opens the possibility of shifting the energy of emitting units on demand and controlling the bimolecular processes they are involved in. To prove this concept, the fluorescence properties of three differently 9,10-substituted anthracene (ANT) derivatives are investigated in a phase-change material (eicosane). The liquid-to-solid transition of the medium leads to an increase of the local dye concentration, a shortening of the intermolecular distances, and the establishment of excited- and ground-state interactions. As a result, a new contribution to the overall luminescence that derives from the downshifted emission (up to 0.7 eV) from excimer-like species is observed. The addition of a second dye (a Pt-porphyrin) reduces the efficiency of excited- and ground-state complexes between fluorophore units, although it does not prevent the formation of multichromophoric aggregates where interactions between Pt-porphyrin and the emissive state of ANT derivatives are observed. The emission of excimer-like species, formed upon solidification of the medium, can be exploited to further down-shift the fluorescence through energy-transfer processes to a suitable energy acceptor, such as rubrene., The University of Perugia and the Ministero Istruzione dell’Università e della Ricerca (MIUR) are thanked for the financial support through the program “Dipartimenti di Eccellenza 2018–2022” (grant AMIS). This work was supported by project MAT2015-70615-R and CTQ2015-65439-R from the Spanish Government and by FEDER funds. ICN2 acknowledges support from the Severo Ochoa Program (MINECO, grant SEV-2017-0706). The work is funded by the CERCA Programme/Generalitat de Catalunya.

International audience; The experimental investigation of the unidirectional motion characterizing the photoisomerization of single-molecule rotary motors requires accessible lab prototypes featuring an electronic circular dichroism (ECD) signal that is sensitive to the geometrical and electronic changes occurring during an ultrafast reactive process. Here we report a combined experimental/computational study of a candidate obtained via the asymmetrization of a light-driven biomimetic molecular switch. We show that the achieved motor has an ECD band that is remarkably sensitive to the isomerization motion, and it is therefore suitable for time-resolved ECD studies. However, we also find that, unexpectedly, the synthesized motor isomerizes on a time scale longer than the subpicosecond time measured for the achiral parent, a result that points to alternative candidates conserving a high reaction speed.

The biomedical translational applications of functionalized nanoparticles require comprehensive studies on their effect on human stem cells. Here, we have tested neat star-shaped mesoporous silica nanoparticles (s-MSN) and their chemically functionalized derivates, we examined nanoparticles (NPs) with similar dimensions but different surface chemistry, due to the amino groups grafted on silica nanoparticles (s-MSN-NH2), and gold nanoseeds chemically adsorbed on silica nanoparticles (s-MSN-Au). The different samples were dropped on glass coverslips to obtain a homogeneous deposition differing only for NPs’ chemical functionalization and suitable for long-term culture of human Bone Marrow–Mesenchymal stem cells (hBM-MSCs) and Adipose stem cells (hASCs). Our model allowed us to demonstrate that hBM-MSCs and hASCs have comparable growth curves, viability, and canonical Vinculin Focal adhesion spots on functionalized s-MSN-NH2 and s-MSN-Au as on neat s-MSN and control systems, but also to show morphological changes on all NP types compared to the control counterparts. The new shape was stem-cell-specific and was maintained on all types of NPs. Compared to the other NPs, s-MSN-Au exerted a small genotoxic effect on both stem cell types, which, however, did not affect the stem cell behavior, likely due to a peculiar stem cell metabolic restoration response.

In this work we report the preparation and characterization of free-standing keratin-based films containing Au/Ag nanorods. The effect of nanorods surface chemistry on the optical and mechanical properties of keratin composite films is fully investigated. Colloid nanorods confer to the keratin films interesting color effects due to plasmonic absorptions of the metal nanostructures. The presence of metal NRs induces also substantial change in the protein fluorescence emission. In particular, the relative contribution of the ordered-protein aggregates emission is enhanced by the presence of cysteine and thus strictly related to the surface chemistry of nanorods. The presence of more packed supramolecular structures in the films containing metal nanorods (in particular cysteine modified ones) is confirmed by ATR measurements. In addition, the films containing nanorods show a higher Young's modulus compared to keratin alone and again the effect is more pronounced for cysteine modified nanorods. Collectively, the reported results indicate the optical and mechanical properties of keratin composites films are related to a common property and can be tuned simultaneously, paving the way to the optimization and improvement of their performances and enhancing the exploitation of keratin composites in highly technological optoelectronic applications.

The use of plasmonic nanomaterials is a challenging strategy to control radiation and radiation-induced processes at a nanometric scale. The localized surface plasmons of metal nanoparticles have been shown to affect the efficiency of a variety of radiative and non-radiative processes occurring in organic molecules. In this contribution, we present an overview of the results obtained through an original approach based on the hierarchical assembly of plasmonic gold colloids on silica templates, covalently doped with organic dyes. The detailed morphological characterization demonstrates the disposition of gold colloids on silica achieved through the tight control of the synthetic conditions. The studies carried out while gradually increasing the concentration of gold nanoparticles allow the detailed investigation of the effects of the progressive addition of plasmonic particles on the photophysical behaviour of organic molecules. In particular, the fluorescence behaviour of three dyes with different spectral properties, namely fluorescein, rhodamine B and 9-aminoacridine, are investigated in the presence of increasing concentrations of gold nanoparticles. In order to fix the distance between the dye and the gold nanoparticles, the dyes are anchored to silica nanoparticles, and the metal colloids are chemically adsorbed on the silica surface. The steady state and time-resolved data are analysed to evaluate the impact of plasmonic nanoparticles on the radiative and non-radiative processes of the dyes; the data provide evidence that the modulation of the fluorescence intensity (enhancement or quenching) can be achieved by changing the concentration of gold colloids. The plasmonic nanostructures can be employed to favour one deactivation process over the others. For example, we demonstrate that the photoinduced formation of reactive oxygen species (ROS) can be enhanced upon the plasmonic engineering of a photosensitizing agent (Protoporphyrin IX, PpIX). The Vis-excitation of silica-PpIX samples in the presence of gold nanoparticles results in a faster and more efficient photoinduced formation of ROS species either in solution or in a hydrogel. The ROS efficiency data and the fluorescence behaviour of PpIX in the presence of gold colloids suggest that the enhancement of the excitation field occurs through a plasmonic effect. For the application of the assembled hybrid materials, further advantages come from the development of photosensitizer-containing hydrogel films that are able to efficiently produce ROS upon visible excitation. Our preliminary results are herein reported and discussed.

Different silica-protoporphyrin IX (PpIX) nanocomposites have been synthesized to evaluate the dependence of singlet oxygen production and bacterial inactivation efficiency on the morphology of the nanomaterials. Modulation of the synthetic procedure allowed obtaining silica nanoparticles with different porosity which were characterized by TEM and spectroscopic analysis after PpIX adsorption. Time-resolved phosphorescence measurements on the different nanoporous samples revealed that the porosity of the nanoparticles plays a pivotal role on the singlet oxygen production and release from the nanoparticles. Thus, apart from the expected decay of singlet oxygen outside the silica matrix, a second component has been observed for the porous materials, attributed to the decay of singlet oxygen inside the pores. The relative efficiency of singlet oxygen production resulted to be higher for the sample with the greatest pores volume. The capability of the nanocomposites to inactivate bacteria was tested in vitro on Staphylococcus aureus strain. Interestingly, the efficiency for singlet oxygen production of the nanocomposites and their bacterial inactivation efficiency followed a different trend, indicating that the relative position of the photosensitizer and the superficial properties of the particles affect the antibacterial activity of the overall system.

Surface-modified ZnAl layered double hydroxides (LDHs) were prepared by reaction of AgNO3, with both ZnAlCl (LDH1) and ZnAlCO3 exchanged on the surface with chloride anions (LDH3). In this way, AgCl nanoparticles with crystalline domains ranging from 40 to 100 nm were grown on the LDH surface. An additional sample was prepared by partial reduction of silver to obtain Ag@AgCl-LDH (LDH2). The composites were tested as catalysts in Rhodamine B (RhB) degradation, wherein LDH2 showed complete cleavage of RhB after 45 min of irradiation versus 70 min needed in the presence of AgCl. This time decreased to 35 min for LDH1 and 15 min for LDH3, underlining the role of the AgCl dimensions and anion in the interlayer region. Studies on the reactive species involved in the degradation process revealed that, for all catalysts, O2&middot, &minus, was the main active species, while, to some extent, holes contribute to the activity of the LDH3. Finally, the composites showed high bactericidal activity, under irradiation, against Escherichia coli, comparable with that of Gentamicin, the positive control. A synergic effect of silver released from the composites and the production of reactive oxygen species was considered.

Silica nanomaterials have been proposed as promising candidates for the delivery of drugs, including purified proteins, thus a systematic investigation on the role of silica surface porosity, for optimal protein loading and release, represents an urgent need. Herein, we report the studies of the loading and releasing processes of different volume-proteins, namely Myoglobin, Bovine Serum Albumin and Factor VIII (FVIII), performed using three porous silica samples. To this aim, silica nanoparticles are prepared through modified sol-gel methods, in which suitable templating and swelling agents are used to enlarge the surface pores from few nm to 25 nm, but retaining the average dimensions of the nanoparticles (80 –90 nm). TEM imaging and Zeta-Potential measurements are used to characterize the silica samples. In this study, the loading process is carried out at pH values close to the isoelectric point of each protein, and the amount of adsorbed protein is quantified and values in the range of μgprotein per mgsilica are obtained. Then, the release profiles are monitored at physiological conditions; for all systems, the release of the proteins is detected, although different behavior are observed. The release profiles are analyzed through the power law equation and through a modular exponential function to achieve information on the mechanism and on kinetics of the release profile. The data show the release from silica particles with small pores follows a diffusion-controlled mechanism, while the kinetic analysis enables to distinguish two-components associated to superficially adsorbed protein and to the portion of protein allocated inside the pores. On the other hand, the particles characterized by the largest pore size (ca. 25 nm) display non-Fickian release profile and a mono-exponential dependency, indicating a mono-modal distribution of the proteins on the silica matrix. Moreover, the conformation or the biological activity of the released proteins has been evaluated through in-vitro methods and the data demonstrate the excellent quality of the recovered proteins. The loading and release data were rationalized in terms of mesoporous structures of the silica nanoparticles in relation to the protein dimensions.

Transmembrane proteins play important roles in intercellular signaling to regulate interactions among the adjacent cells and influence cell fate. The study of interactions between membrane proteins and nanomaterials is paramount for the design of nanomaterial-based therapies. In the present work, the fluorescence properties of the transmembrane receptor Notch2 have been investigated. In particular, the steady-state and time-resolved fluorescence methods have been used to characterize the emission of tryptophan residues of Notch2 and then this emission is used to monitor the effect of silver colloids on protein behavior. To this aim, silver colloids are prepared with two different methods to make sure that they bear hydrophilic (citrate ions, C-AgNPs) or hydrophobic (dodecanethiol molecules, D-AgNPs) capping agents. The preparation procedures are tightly controlled to obtain metal cores with similar size distributions (7.4 ± 2.5 and 5.0 ± 0.8 nm, respectively), thus, making the comparison of the results easier. The occurrence of strong interactions between Notch2 and D-AgNPs is suggested by the efficient and statistically relevant quenching of the stationary protein emission already at low nanoparticle (NP) concentrations (ca. 12% quenching with [D-AgNPs] = 0.6 nM). The quenching becomes even more pronounced (ca. 60%) when [D-AgNPs] is raised to 8.72 nM. On the other hand, the addition of increasing concentrations of C-AgNPs to Notch2 does not affect the protein fluorescence (intensity variations below 5%) indicating that negligible interactions are taking place. The fluorescence data, recorded in the presence of increasing concentrations of silver nanoparticles, are then analyzed through the Stern-Volmer equation and the sphere of action model to discuss the nature of interactions. The effect of D-AgNPs on the fluorescence decay times of Notch2 is also investigated and a decrease in the average decay time is observed (from 4.64 to 3.42 ns). The observed variations of the stationary and time-resolved fluorescence behavior of the protein are discussed in terms of static and collisional interactions. These results document that the capping shell is able to drive the protein-particle interactions, which likely have a hydrophobic nature.

Photodynamic treatments represent a non-invasive tool to intervene in the cell cycle, only when needed, but high excitation power is an important limitation. In this work, protoporphyrin IX (PpIX) is covalently anchored to the surface of silica particles. The hybrid colloids are prepared with different photosensitizer loadings and characterized by TEM, SEM-EDX and spectroscopic methods. The visible excitation of the colloidal samples generates reactive oxygen species, which are quantified by use of a specific chemical scavenger agent (1,3-diphenylisobenzofuran). The determined efficiencies depend on the PpIX loading, being higher in the sample where the aggregation is reduced. To enhance further the photosensitizing performance of silica-PpIX samples, increasing amounts of gold nanoparticles are conjugated to the silica surface in order to exploit the antenna effect of plasmonic nanostructures. The visible excitation of silica-PpIX systems in the presence of gold nanoparticles results in a faster and more efficient photoinduced formation of ROS species reaching a 230 % enhancement of ROS photosensitization when 1013 Au nanoparticles mL−1 (corresponding to circa 75 ppm of gold) are present. The efficiency data are discussed in terms of plasmonic enhancement of the excitation field.

The preparation of tailored nanomaterials able to support cell growth and viability is mandatory for tissue engineering applications. In the present work, silica nanoparticles were prepared by a sol-gel procedure and were then functionalized by condensation of amino groups and by adsorption of silver nanoparticles. Transmission electron microscopy (TEM) imaging was used to establish the morphology and the average dimensions of about 130 nm, which were not affected by the functionalization. The three silica samples were deposited (1 mg/mL) on cover glasses, which were used as a substrate to culture adult human bone marrow-mesenchymal stem cells (hBM-MSCs) and human adipose-derived stem cells (hASCs). The good cell viability over the different silica surfaces was evaluated by monitoring the mitochondrial dehydrogenase activity. The analysis of the morphological parameters (aspect ratio, cell length, and nuclear shape Index) yielded information about the interactions of stem cells with the surface of three different nanoparticles. The data are discussed in terms of chemical properties of the surface of silica nanoparticles.