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Triiodide (I3−) is a species well-known to influence the nature of perovskite materials. Here, we highlight possible and unexpected sources of I3−, i.e. the iodide (I−) salt solutions used for the synthesis of metal-halide perovskites.

ispartof: ACS SUSTAINABLE CHEMISTRY & ENGINEERING vol:10 issue:28 pages:9123-9130 status: published

The developments made towards increasingly photoactive copper(I) complexes has led to their use in many applications involving light, in particular light emission or photocatalytic activities. Herein, we describe an unprecedented in-depth study of the photophysical properties of two of the most used copper(I) photosensitizers, [Cu(bcp)(Xantphos)]+ and [Cu(bcp)(DPEphos)]+ (bcp = bathocuproine, Xantphos = 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene, DPEphos = Bis[(2-diphenylphosphino)phenyl]ether). This study combines traditional spectroscopic techniques with state-of-the-art femtosecond time-resolved transient absorption and fluorescence up-conversion spectroscopy and is further supported by quantum-chemical calculations. This combined analysis hints at the presence of a low-lying ligand-centered dark triplet state which plays a crucial role by acting as a reservoir for the excited hetereloptic copper(I) complexes.

The aim of this work is to investigate the possibility of engineering desired molecular sp2 structures in graphene oxide, via controlled oxidation of graphite powder, in order to achieve tunable chemical and microstructural properties useful for optoelectronics or sensing applications. Specifically, GO powder is obtained by a modified Hummers method, by using different concentrations of potassium permanganate (KMnO4) in order to change the number of oxygen functionalities in the graphitic structure. Then, a successive alkaline treatment is performed by increasing the KOH concentration. The alkaline treatment induces a noticeable variation of the GO microstructural and chemical properties, which is accompanied by a strong enhancement of photoluminecence. PL and PLE measurements reveal that the configuration of electronic energy states changes as a function of the KMnO4 and KOH concentration, by introducing further electronic n levels available for n→π* transitions. In particular, the number of sp2 small domains embedded among oxygen–sp3 domains, increases under the KOH treatment, due to the addition of OH groups. Most of these sp2 domains are lifted-off from GO and thrown away in the surnatant giving it high blue photoluminescence excited at λexc ∼ 319 nm. The employ of combined spectroscopy techniques allows a deep investigation of the microstructural and chemical changes induced by chemical treatments, opening the way to the fine tuning of GO functional properties.

HBDI-like chromophores represent a novel set of biomimetic switches mimicking the fluorophore of the green fluorescent protein that are currently studied with the hope to expand the molecular switch/motor toolbox. However, until now members capable of absorbing visible light in their neutral (i. e. non-anionic) form have not been reported. In this contribution we report the preparation of an HBDI-like chromophore based on a 3-phenylbenzofulvene scaffold capable of absorbing blue light and photoisomerizing on the picosecond timescale. More specifically, we show that double-bond photoisomerization occurs in both the E-to-Z and Z-to-E directions and that these can be controlled by irradiating with blue and UV light, respectively. Finally, as a preliminary applicative result, we report the incorporation of the chromophore in an amphiphilic molecule and demonstrate the formation of a visible-light-sensitive nanoaggregated state in water.

The use of light-responsive proteins to control both living or synthetic cells, is at the core of the expanding fields of optogenetics and synthetic biology. It is thus apparent that a richer reaction toolbox for the preparation of such systems is of fundamental importance. Here, we provide a proof-of-principle demonstration that Morita-Baylis-Hillman adducts can be employed to perform a facile site-specific, irreversible and diastereoselective click-functionalization of a lysine residue buried into a lipophilic binding pocket and yielding an unnatural chromophore with an extended π-system. In doing so we effectively open the path to the in vitro preparation of a library of synthetic proteins structurally reminiscent of xanthopsin eubacterial photoreceptors. We argue that such a library, made of variable unnatural chromophores inserted in an easy-to-mutate and crystallize retinoic acid transporter, significantly expand the scope of the recently introduced rhodopsin mimics as both optogenetic and "lab-on-a-molecule" tools.

Oil-in-silica capsules enable triplet–triplet annihilation radiation up-conversion in air equilibrated conditions and their use to achieve controlled intensity modulated emission.

Silver@Hydroxyapatite functionalized calcium carbonate composites have been prepared through different sustainable methods, without involving the use of organic solvents and additional reagents. The composites were characterized by X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy, spectrophotometric measurements and X-ray photoemission spectroscopy. From the characterization techniques, the obtained nanoparticles resulted constituted essentially by Ag3PO4 nanostructures, whose size varied from 70 to 100 nm and were uniformly distributed on the calcium carbonate surface. Upon VIS irradiation, the formation of plasmonic nanostructures with a more defined dimensional distribution and reduced size could be obtained, as a prove of a partial silver reduction. All composites exhibited good antimicrobial and antibiofilm activities against Staphylococcus aureus and Pseudomonas aeruginosa whereas they showed low cytotoxicity effects towards human skin keratinocytes and human fibroblasts. These results enable these composites to be promising candidates for biomedical and pharmaceutical applications.

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.

In the present work, composite materials very promising for biomedical and pharma-ceutical applications were investigated. They are composed of silver nanoparticles (Ag NPs) in a matrix constituted of calcium carbonate functionalized with hydroxyapatite (HA-FCC). The composites were obtained by different synthesis methods, starting from a mixture of the silver acetate with HA-FCC (using adsorption or mixing in wet conditions methods) and then treating them by exposure to visible light or calcination to promote the silver reduction, a synthetic procedure based on ultrasound-assisted reduction with NaBH4 or citrate was also carried out. The characterization by X-ray photoelectron spectroscopy and reflected electron energy loss spectroscopy analysis also involved the reference sample of HA-FCC matrix. Then the morphology of the Ag NPs and the crystalline structure of HA-FCC were studied by transmission electron microscopy and X-ray diffraction, respectively. To assess the effectiveness of the different methods on silver reduction, the Auger parameters α’ were calculated and compared. The use of this methodology based on the Auger parameter is neither trivial nor ordinary. We demonstrate its validity since the different values of this parameter allow to identify the oxidation state of silver and consequently to evaluate the formation yield of metallic Ag NPs in the HA-FCC matrix and the effectiveness of the different reduction methods used.

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.

Halloysite (Hal) has already been proposed as a support for zinc oxide nanoparticles synthesis due to the possibility of adsorbing ZnO on its internal and external tubular surface, but no attention has been devoted to evaluate the effect of this support on radiation screening capabilities. In this paper, zinc oxide nanoparticles were obtained by three different methods in the presence of Hal. Adsorption, solvent evaporation, and solvothermal methods were used. Quantitative Zn was determined by inductively coupled plasma optical emission spectrometry (ICP-OES), and nanocomposites were characterized by X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). This characterization elucidated that three different nanocomposites were obtained. In particular, when the adsorption method was used, small and quite uniform sized (10-30 nm) zinc oxide nanoparticles confined inside the Hal nanotubules were obtained. The UV-vis spectra of these nanocomposites revealed their ability to interact with a wide portion of UV-vis radiation which leads to enhanced sun screening performance. © 2019 American Chemical Society.

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.

Folic acid (FA) is a key factor in the physiological processes of cell metabolism; as it is involved in DNA synthesis and repair, it can be used in the treatment of aged and photo-damaged skin. The main drawbacks associated to FA use, particularly for topical applications, are the limited solubility and the sensitivity to UV rays. Hybrids of FA with two kinds of layered double hydroxides (ZnAl-LDH and MgAl-LDH) were prepared and characterized showing suitable particle size, flow properties and UV photoprotection. The introduction of FA-LDHs in the external water phase of O/W emulgels produced an enhancement of their flow properties; moreover, the spectrophotometric analyses showed that very good photostability is maintained even after their introduction into the formulations. In-vitro release studies showed that the FA-LDH containing emulgels promoted a sustained FA release as expected. Finally, the safety of FA-LDH was evaluated by in-vitro studies performed on human keratinocytes (HaCaT) and human primary dermal fibroblasts (as a skin representative). The obtained results showed a high cytotoxic effect of ZnAl-LDH-FA in both cell lines.

Most targeting strategies of anticancer drug delivery systems (DDSs) rely on the surface functionalization of nanocarriers with specific ligands, which trigger the internalization in cancer cells via receptor-mediated endocytosis. The endocytosis implies the entrapment of DDSs in acidic vesicles (endosomes and lysosomes) and their eventual ejection by exocytosis. This process, intrinsic to eukaryotic cells, is one of the main drawbacks of DDSs because it reduces the drug bioavailability in the intracellular environment. The escape of DDSs from the acidic vesicles is, therefore, crucial to enhance the therapeutic performance at low drug dose. To this end, we developed a multifunctionalized DDS that combines high specificity towards cancer cells with endosomal escape capabilities. Doxorubicin-loaded mesoporous silica nanoparticles were functionalized with polyethylenimine, a polymer commonly used to induce endosomal rupture, and hyaluronic acid, which binds to CD44 receptors, overexpressed in cancer cells. We show irrefutable proof that the developed DDS can escape the endosomal pathway upon polymeric functionalization. Interestingly, the combination of the two polymers resulted in higher endosomal escape efficiency than the polyethylenimine coating alone. Hyaluronic acid additionally provides the system with cancer targeting capability and enzymatically controlled drug release. Thanks to this multifunctionality, the engineered DDS had cytotoxicity comparable to the pure drug whilst displaying high specificity towards cancer cells. The polymeric engineering here developed enhances the performance of DDS at low drug dose, holding great potential for anticancer therapeutic applications. ispartof: SCIENTIFIC REPORTS vol:9 issue:1 ispartof: location:England status: published

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.

Radiation upconversion can be an elegant and efficient strategy to minimize waste in energy harvesting and storage processes. The upconversion based on triplet–triplet annihilation processes of molecular dyes is a very versatile approach, but it requires a systematic photophysical characterization of the systems to optimize the upconversion yields and develop materials for technological applications. This paper represents an overview of the work carried out in our laboratories for the study and characterization of a molecular dye pair, 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II) (PtOEP) and 1,3,6,8-tetraphenylpyrene (TPPy), suitable as the sensitizer and emitter, respectively, in a triplet–triplet annihilation based upconversion process. The investigation has been carried out in various media with increasing complexity. First, we used the dye pair to characterize the UC-efficiencies in homogeneous solvents of different viscosities and in oil-in-water microemulsions; then we explored the possibility to achieve upconversion in solid materials, like nanostructured silica matrices and liquid filled microcapsules. The possibility to achieve upconversion emission even in confined and rigid media has been confirmed and can inspire further applications of the process., This work was supported by the University of Perugia. F. Ortica gratefully acknowledges INFN for financial support. ICN2 ackowledges support of the MAT2015-70615-R project from the spanish Government, by FEDER funds, the Severo Ochoa program (MINECO, Grant SEV-2013-0295) and CERCA programme/Generalitat de Catalunya. G. Massaro thanks the University of Perugia for the Erasmus fellowship.

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.

Alginate films containing pyrogenic silica supported silver nanoparticles were prepared as potential wound dressings. First silica supported silver nanoparticles (CAB-O-SIL-Ag) were prepared via solid state sintering route without the use of any solvent and reducing agent. The obtained composite was characterized by X-ray powder diffraction, transmission electron microscopy and UV–vis spectroscopy which evidenced the presence of 8–20 nm spherical silver nanoparticles uniformly distributed and grown on the silica surface. Then the CAB-O-SIL-Ag was used as filler to prepare alginate films by casting method and successive gelation. Films with two different silver concentrations were prepared. They showed good hydration properties and a very slow silver release. Films exhibited antimicrobial and antibiofilm activities against Staphylococcus aureus and Pseudomonas aeruginosa and showed no cytotoxicity towards human skin keratinocytes and human fibroblasts HuDe.

Authors sincerely acknowledge Morena Nocchetti for X-ray patterns and registration and Marco Marani for technical assistance from the Department of Pharmaceutical Sciences. Authors wish to thank Simonetta De Angelis from ASL N. 1 (Città di Castello, Perugia, Italy), for providing pig skin samples., Ketoprofen (KET) represents one of the most common drugs used in the topical treatment of pain and inflammations. However, its potential is rather limited due to the very low solubility and photochemical instability. The local administration of KET by conventional products, such as gels, emulgels, creams, and foams, does not guarantee an efficacious and safe treatment because of its low absorption (due to low solubility) and its sensitivity to UV rays. The photodegradation of KET makes many photoproducts responsible for different adverse effects. In the present work, KET was intercalated into the lamellar anionic clay ZnAl-hydrotalcite (ZnAl-HTlc), obtaining the hybrid ZnAl-KET with improved stability to UV rays and water solubility in comparison to the crystalline form (not intercalated KET). The hybrid was then formulated in autoadhesive patches for local pain treatment. The patches were prepared by casting method starting from a hydrogel based on the biocompatible and bioadhesive polymer NaCMC (Sodium carboxymethycellulose) and glycerol as a plasticizing agent. The introduction of ZnAl-KET in the patch composition demonstrated the improvement in the mechanical properties of the formulation. Moreover, a sustained and complete KET release was obtained within 8 h. This allowed reducing the frequency of anti-inflammatory administration, compared to the conventional formulations

Placed at the junction of laser-scanning and probe-scanning techniques, scattering scanning near-field optical microscopy (s-SNOM) is a promising tool for the optical investigation of surfaces at nanoscale resolution. In this work we expand the current possibilities of representing s-SNOM data by coupling typical s-SNOM results (amplitude and phase images) with the phasor representation method, an extremely powerful approach for complex data analysis. Our results demonstrate that representing s-SNOM data in the phasor space can be very useful for surface characterization of different types of materials and can be successfully used for distinguishing distinct materials (or distinct species of the same material). Phasor representation of s-SNOM data proves thus to augment this technique's potential for optically investigating surfaces at nanoscale. In our opnnion, thewidespread of such approaches could bring significant added value in applications where identifying and understanding the physicochemical properties of advanced materials and biological samples at nanoscale is important.

The modification of amyloid fibrils cytotoxicity through exogenous nanomaterials is crucial to understand the processes controlling the role of protein aggregation in the related diseases. The influence of nanoparticles on amyloid stability yields great interest due to the small size and high surface area-to-volume ratio of nanoparticles. Various physico-chemical parameters play a role in the interaction of proteins and nanoparticles in solution, thus influencing the disaggregation of preformed fibrils. We have examined the influence of two kinds of metallic nanoparticles on lysozyme amyloid fibrils using a multi-technique approach and focalized their impact on cytotoxicity on human neuroblastoma cells (SH-SY5Y). In particular, fluorescence, infrared and circular dichroism spectroscopies, optical and atomic force microscopy experiments have been carried out; the results are analyzed to rationalize the effects of these complexes on neural cell viability. It is remarkable, that the fibrils in the presence of AuNPs, unlike fibrils alone or with AgNPs, do not generate a significant cytotoxic effect even at high concentration and an amyloid degradation effect is visible.

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.

Glioblastoma multiforme (GBM) is the most frequent malignant brain tumor characterized by highly heterogeneous subpopulations. In order to reveal the heterogeneous cell response, single cell analysis is an essential requirement. In this study, optical microscopy and Raman microspectroscopy were used to follow the stress response of U251 single cells adherent on a silicon substrate. Cultured cells on silicon substrate were treated with hydrogen peroxide to promote apoptosis. Under these conditions expected changes occurred after a few hours and were revealed by the reduction of cytochrome c, lipid, nucleic acid and protein Raman signals: this ensured the possibility to analyse U251 cell line as grown on Si substrate, and to monitor the response of single cells to stress conditions. As a consequence, we used microRaman to monitor the effects induced by nutrient depletion: a fast change of Raman spectra showed two different sub-populations of sensible and resistant U251 cells. Furthermore, spectral variations after DMSO addition were associated to volume changes and confirmed by morphological analysis. Thus, our results highlight the sensitivity of Raman microspectroscopy to detect rapid variations of macromolecule concentration due to oxidative stress and/or cell volume changes at the single cell level.

Methylammonium Lead Iodide perovskite (MAPbI3) is today considered the most promising component for highly efficient third generation solar cells. However, the lifetime of the solar devices is strongly affected by the stability of the MAPbI3 films towards humidity, UV irradiation and temperature. The search for efficient protective additives to be used for building up composite perovskite films with enhanced stability is a topic of great interest in the scientific community. In the present paper we have applied a layered zirconium phosphate-phosphonate based on N,N-phosphonomethyl glycine, exfoliated in thin nanosheets (NS), as additive for the stabilization of MAPbI3 crystalline films towards humidity, UV-irradiation and temperature changes. Notably, the additive resulted extremely efficient to prevent degradation of the perovskite film, preserving the optical and structural properties and avoiding the phase transitions normally observed due to temperature increase.

This work shows that the active interaction between human umbilical cord matrix stem cells and Poly ( l -lactide)acid (PLLA) and PLLA/Multi Walled Carbon Nanotubes (MWCNTs) nanocomposite films results in the stem cell assembly as a spheroid conformation and affects the stem cell fate transition. We demonstrated that spheroids directly respond to a tunable surface and the bulk properties (electric, dielectric and thermal) of plain and nanocomposite PLLA films by triggering a mechanotransduction axis. This stepwise process starts from tethering of the cells' focal adhesion proteins to the surface, together with the adherens junctions between cells. Both complexes transmit traction forces to F-Actin stress fibres that link Filamin-A and Myosin-IIA proteins, generating a biological scaffold, with increased stiffening conformation from PLLA to PLLA/MWCNTs, and enable the nucleoskeleton proteins to boost chromatin reprogramming processes. Herein, the opposite expression of NANOG and GATA6 transcription factors, together with other lineage specification related proteins, steer spheroids toward an Epiblast-like or Primitive Endoderm-like lineage commitment, depending on the absence or presence of 1 wt% MWCNTs, respectively. This work represents a pioneering effort to create a stem cell/material interface that can model the stem cell fate transition under growth culture conditions.

The understanding of charge carrier dynamics in hybrid materials based on colloidal semiconductor nanocrystals (or quantum dots) and organic moieties is fundamental for the design of efficient photonic and photovoltaic devices. In the present work, we investigate the interactions occurring between CdTe quantum dots, capped with a strong capping agent such as 3-mercaptopropionic acid, and a well known electron acceptor such as methylviologen molecule. The nature of the interactions and of exciton dynamics is investigated by stationary and time-resolved spectroscopies. Luminescence data recorded in presence of increasing methylviologen concentrations, indicate that the organic molecule is able to statically interact with the surface sites of CdTe quantum dots; a biphasic interaction behavior is evidenced by determining the apparent association constants. These latter are obtained through the analysis of luminescence data, and values in the range 10(3)-10(4) are determined. The nature of the interactions is characterized by nanosecond and femtosecond transient absorption spectroscopies, to clarify the dynamics and the conditions able to foster charge mobility. Nanosecond flash photolysis measurements, carried out upon quantum dots excitation, shows the absorption of methylviologen radical cation specie at 605 nm, suggesting the occurrence of electron transfer from CdTe nanocrystals to the organic acceptor; the relatively long decay time of the transient signal (10.3 mu s) indicates that back electron transfer processes are negligible. Ultrafast transient absorption measurements confirm the occurrence of an ultrafast electron transfer process; spectral and kinetic analysis of the transient data show that methylviologen radical cation is formed almost instantaneously on the ps-time scale but mainly when the samples are pumped in the energy continuum at 400 nm. This finding suggests that electron mobility from the nanocrystals to the organic units is achieved mainly when the excitonic states possess an excess of energy. The comparison of the kinetic behaviour of the signals at increasing methylviologen concentrations indicates that the electron transfer process competes with the radiative exciton recombination. In addition, the kinetic data suggests that surface trapping and Auger recombination processes might slow down the charge mobility. (C) 2017 Elsevier B.V. All rights reserved.