Physical and chemical properties and degradation of MAPbBr3 films on transparent substrates.

To date, the potential exploitation of hybrid organic-inorganic perovskites (HOIPs) in photovoltaic technologies has been significantly hampered by their poor environmental stability. HOIP degradation can be triggered by conventional operational environments, with excessive heating and exposure to oxygen and moisture significantly reducing the performances of HOIP-based solar cells. An imperative need emerges for a thorough investigation on the impact of these factors on the HOIP stability. In this work, the degradation of methylammonium lead bromide (CH3NH3PbBr3) thin films, deposited via spin-coating on indium tin oxide (ITO) and strontium titanate (STO) substrates, was investigated by combining Raman and ultraviolet-visible (UV-Vis) absorption spectroscopy, as well as optical and fluorescence microscopy. We assessed the physical and chemical degradation of the films occurring under diverse preservation conditions, shedding light on the byproducts emerging from different degradation pathways and on the optimal HOIP preservation conditions.

Polymorphism and Ligand Binding Modulate Fast Dynamics of Human Telomeric G-Quadruplexes.

Telomeric G-quadruplexes (G4s) are promising targets in the design and development of anticancer drugs. Their actual topology depends on several factors, resulting in structural polymorphism. In this study, we investigate how the fast dynamics of the telomeric sequence AG3(TTAG3)3 (Tel22) depends on the conformation. By using Fourier transform Infrared spectroscopy, we show that, in the hydrated powder state, Tel22 adopts parallel and mixed antiparallel/parallel topologies in the presence of K+ and Na+ ions, respectively. These conformational differences are reflected in the reduced mobility of Tel22 in Na+ environment in the sub-nanosecond timescale, as probed by elastic incoherent neutron scattering. These findings are consistent with the G4 antiparallel conformation being more stable than the parallel one, possibly due to the presence of ordered hydration water networks. In addition, we study the effect of Tel22 complexation with BRACO19 ligand. Despite the quite similar conformation in the complexed and uncomplexed state, the fast dynamics of Tel22-BRACO19 is enhanced compared to that of Tel22 alone, independently of the ions. We ascribe this effect to the preferential binding of water molecules to Tel22 against the ligand. The present results suggest that the effect of polymorphism and complexation on the G4 fast dynamics is mediated by hydration water.

Influence of Cortisol on the Fibril Formation Kinetics of Aß42 Peptide: A Multi-Technical Approach.

Amyloid-ß peptide (Aß) aggregates are known to be correlated with pathological neurodegenerative diseases. The fibril formation process of such peptides in solution is influenced by several factors, such as the ionic strength of the buffer, concentration, pH, and presence of other molecules, just to mention a few. In this paper, we report a detailed analysis of in vitro Aß42 fibril formation in the presence of cortisol at different relative concentrations. The thioflavin T fluorescence assay allowed us to monitor the fibril formation kinetics, while a morphological characterization of the aggregates was obtained by atomic force microscopy. Moreover, infrared absorption spectroscopy was exploited to investigate the secondary structure changes along the fibril formation path. Molecular dynamics calculations allowed us to understand the intermolecular interactions with cortisol. The combined results demonstrated the influence of cortisol on the fibril formation process: indeed, at cortisol-Aß42 concentration ratio (ρ) close to 0.1 a faster organization of Aß42 fragments into fibrils is promoted, while for ρ = 1 the formation of fibrils is completely inhibited.

Photons for Photography: A First Diagnostic Approach to Polaroid Emulsion Transfer on Paper in Paolo Gioli's Artworks.

The aim of this research is to study and diagnose for the first time the Polaroid emulsion transfer in the contemporary artist Paolo Gioli's artworks to provide preliminary knowledge about the materials of his artworks and the appropriate protocols which can be applied for future studies. The spectral analysis performed followed a multi-technical approach first on the mock-up samples created following Gioli's technique and on one original artwork of Gioli, composed by: FORS (Fiber Optics Reflectance), Raman, and FTIR (Fourier-Transform InfraRed) spectroscopies. These techniques were chosen according to their completely non-invasiveness and no requirement for sample collection. The obtained spectra from FTIR were not sufficient to assign the dyes found in the transferred Polaroid emulsion. However, they provided significant information about the cellulose-based materials. The most diagnostic results were obtained from FORS for the determination of the dye developers present in the mock-up sample which was obtained from Polacolor Type 88 and from Paolo Gioli's original artwork created with Polacolor type 89.

The Puzzling Problem of Cardiolipin Membrane-Cytochrome c Interactions: A Combined Infrared and Fluorescence Study.

The interaction of cytochrome c (cyt c) with natural and synthetic membranes is known to be a complex phenomenon, involving both protein and lipid conformational changes. In this paper, we combined infrared and fluorescence spectroscopy to study the structural transformation occurring to the lipid network of cardiolipin-containing large unilamellar vesicles (LUVs). The data, collected at increasing protein/lipid ratio, demonstrate the existence of a multi-phase process, which is characterized by: (i) the interaction of cyt c with the lipid polar heads; (ii) the lipid anchorage of the protein on the membrane surface; and (iii) a long-distance order/disorder transition of the cardiolipin acyl chains. Such effects have been quantitatively interpreted introducing specific order parameters and discussed in the frame of the models on cyt c activity reported in literature.

Grazing-angle reflectivity setup for the low-temperature infrared spectroscopy of two-dimensional systems.

A new optical setup is described that allows the reflectivity at grazing incidence to be measured, including ultrathin films and two-dimensional electron systems (2DES) down to liquid-helium temperatures, by exploiting the Berreman effect and the high brilliance of infrared synchrotron radiation. This apparatus is well adapted to detect the absorption of a 2DES of nanometric thickness, namely that which forms spontaneously at the interface between a thin film of LaAlO3 and its SrTiO3 substrate, and to determine its Drude parameters.

Infrared Spectroscopy of the Topological Surface States of Bi_{2}Se_{3} by Use of the Berreman Effect.

The Berreman effect (BE) allows one to study the electrodynamics of ultrathin conducting films at the surface of dielectrics by use of grazing-angle infrared spectroscopy and polarized radiation. Here, we first apply the BE to the two-dimensional electron system (2DES) at the interface between a high-purity film of the topological insulator Bi_{2}Se_{3} and its sapphire substrate. We determine for the 2DES a charge density n_{s}=(8±1)×10^{12} cm^{-2}, a thickness d=0.6±0.2 nm, and a mobility µ^{IR}=290±30 cm^{2}/V s. Within errors, all of these parameters result in being independent of temperature between 300 and 10 K. These findings consistently indicate that the 2DES is formed by topological surface states, whose infrared response is then directly observed here.

Heterogeneity of the Transmembrane Protein Conformation in Purple Membranes Identified by Infrared Nanospectroscopy.

Cell membranes are intrinsically heterogeneous, as the local protein and lipid distribution is critical to physiological processes. Even in template systems embedding a single protein type, like purple membranes, there can be a different local response to external stimuli or environmental factors, resulting in heterogeneous conformational changes. Despite the dramatic advances of microspectroscopy techniques, the identification of the conformation heterogeneity is still a challenging task. Tip-enhanced infrared nanospectroscopy is here used to identify conformational changes connected to the hydration state of the transmembrane proteins contained in a 50 nm diameter cell membrane area, without the need for fluorescent labels. In dried purple membrane monolayers, areas with fully hydrated proteins are found among large numbers of molecules with randomly distributed hydration states. Infrared nanospectroscopy results are compared to the spectra obtained with diffraction-limited infrared techniques based on the use of synchrotron radiation, in which the diffraction limit still prevents the observation of nanoscale heterogeneity.

Exogenous control over intracellular acidification: Enhancement via proton caged compounds coupled to gold nanoparticles.

The pH regulation has a fundamental role in several intracellular processes and its variation via exogenous compounds is a potential tool for intervening in the intracellular processes. Proton caged compounds (PPCs) release protons upon UV irradiation and may efficiently provoke intracellular on-command acidification. Here, we explore the intracellular pH variation, when purposely synthesized PCCs are coupled to gold nanoparticles (AuNPs) and dosed to HEK-293 cells. We detected the acidification process caused by the UV irradiation by monitoring the intensity of the asymmetric stretching mode of the CO(2) molecule at 2343 cm(-1). The comparison between free and AuNPs functionalized proton caged compound demonstrates a highly enhanced CO(2) yield, hence pH variation, in the latter case. Finally, PCC functionalized AuNPs were marked with a purposely synthesized fluorescent marker and dosed to HEK-293 cells. The corresponding fluorescence optical images show green grains throughout the whole cytoplasm.

Modulating intracellular acidification by regulating the incubation time of proton caged compounds.

A proton caged compound, the 1-(2-nitrophenyl)- ethylhexadecyl sulfonate (HDNS), was dosed into HEK-293 at different incubation times. Samples were irradiated with filtered UV light for inducing photolysis of the HDNS and then probed by infrared spectroscopy. The intracellular acidification reaction can be followed by monitoring the consequent CO2 peak intensity variation. The total CO2 produced is similar for all the samples, hence it is only a function of the initial HDNS concentration. The way it is achieved, though, is different for the different incubation times and follows kinetics, which results in a combination of a linear CO2 increase and a steep CO2 increase followed by a decay. This is interpreted in terms of confinement of the HDNS into intracellular vesicles of variable average size and sensitive to UV light when they reach critical dimensions.

An integrated superhydrophobic-plasmonic biosensor for mid-infrared protein detection at the femtomole level.

In this work we present an integrated biosensor that enables FTIR (Fourier Transform-Infrared) detection of analytes contained in diluted solutions. The fabricated nanosensor allows for the detection of proteins through the identification of the fine structure of their amide I and II bands, up to the nanomolar concentration range. We exploited two distinct effects to enhance the sensitivity: (i) the concentration effect due to the presence of the superhydrophobic surface that conveys molecules dispersed in solution directly inside the focus of a FTIR spectromicroscope; (ii) the plasmonic resonance of the nanoantenna array that provides electromagnetic field enhancement in the amide I and II spectral region (1500-1700 cm(-1)). We demonstrate the detection of ferritin in the nanomolar concentration range, a blood protein that is usually available in small amounts in typical blood samples.

Far-Infrared Signatures for a Two-Step Pressure-Driven Metallization in Transition Metal Dichalcogenides.

We present a high-pressure investigation of the semiconductor-to-metal transition in MoS2 and WS2 carried out by synchrotron-based far-infrared spectroscopy, to reconcile the controversial estimates of the metallization pressure found in the literature and gain new insight into the mechanisms ruling this electronic transition. Two spectral descriptors are found indicative of the onset of metallicity and of the origin of the free carriers in the metallic state: the absorbance spectral weight, whose abrupt increase defines the metallization pressure threshold, and the asymmetric line shape of the E1u peak, whose pressure evolution, interpreted within the Fano model, suggests the electrons in the metallic state originate from n-type doping levels. Combining our results with those reported in the literature, we hypothesize a two-step mechanism is at work in the metallization process, in which the pressure-induced hybridization between doping and conduction band states drives an early metallic behavior, while the band gap closes at higher pressures.

Signatures of Polaron Dynamics in Photoexcited MAPbBr3 by Infrared Spectroscopy.

Hybrid organic-inorganic perovskites (HOIPs) have attracted considerable attention in the past years as photoactive materials for low-cost, high-performance photovoltaics. Polaron formation through electron-phonon coupling has been recognized as the leading mechanism governing charge carrier transport and recombination in HOIPs. In this work, two types of MAPbBr3 film samples deposited on different substrates (transparent insulating SrTiO3 and a heterostructure mimicking a functioning photovoltaic cell) were photoexcited with above-bandgap radiation at 450 nm, and the effects of illumination on the sample were analyzed in the infrared region. The infrared absorbance detected at different powers of the photoexciting laser allowed us to obtain an estimate of the characteristic decay time of photoexcited polaron population of the order of 100-1000 ns. When focusing on the absorption features of the MA molecular cation in the region of the NH stretching modes, we observed the influence of hydrogen bonding and the effect of the polaron dynamics on the cation reorientation.

Legume Proteins and Peptides as Compounds in Nutraceuticals: A Structural Basis for Dietary Health Effects.

In the current climate of food security, quality aspects of legume crops have primary market economic and health impact. Legume proteins and peptides have been discovered to have a role far beyond supplying amino acids for growth and maintenance of body tissues. Several proteins (enzymatic inhibitors, lectins, storage globulins) and peptides derived from them (lunasin, hydrophobic peptides) have shown anticarcinogenic, hypocholesterolemic, glucose-lowering, antioxidant, antimicrobial, and immunostimulant properties. Further understanding of how structural features of legume proteins affect in vivo digestion and production of bioactive sequences represents a key step in the valorization of nutraceutical potentiality of legume proteins and peptides derived from them. In this work, the relationship between structure and bioavailability of protein and peptides are reviewed and discussed.

Syntheses of APTMS-Coated ZnO: An Investigation towards Penconazole Detection.

Extrinsic chemiluminescence can be an efficient tool for determining pesticides and fungicides, which do not possess any intrinsic fluorescent signal. On this basis, (3-aminopropyl) trimethoxysilane (APTMS)-coated ZnO (APTMS@ZnO) was synthesized and tested as an extrinsic probe for the fungicide penconazole. Several synthetic routes were probed using either a one-pot or two-steps method, in order to ensure both a green synthetic pathway and a good signal variation for the penconazole concentration. The synthesized samples were characterized using X-ray diffraction (XRD), infrared (IR), Raman and ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM) imaging and associated energy-dispersive X-ray (EDX) analysis. The average size of the synthesized ZnO nanoparticles (NPs) is 54 ± 10 nm, in line with previous preparations. Of all the samples, those synthesized in two steps, at temperatures ranging from room temperature (RT) to a maximum of 40 °C, using water solvent (G-APTMG@ZnO), appeared to be composed of nanoparticles, homogeneously coated with APTMS. Chemiluminescence tests of G-APTMG@ZnO, in the penconazole concentration range 0.7-1.7 ppm resulted in a quenching of the native signal between 6% and 19% with a good linear response, thus indicating a green pathway for detecting the contaminant. The estimated detection limit (LOD) is 0.1 ± 0.01 ppm.

Low-Temperature Stability and Sensing Performance of Mid-Infrared Bloch Surface Waves on a One-Dimensional Photonic Crystal.

The growing need for new and reliable surface sensing methods is arousing interest in the electromagnetic excitations of ultrathin films, i.e., to generate electromagnetic field distributions that resonantly interact with the most significant quasi-particles of condensed matter. In such a context, Bloch surface waves turned out to be a valid alternative to surface plasmon polaritons to implement high-sensitivity sensors in the visible spectral range. Only in the last few years, however, has their use been extended to infrared wavelengths, which represent a powerful tool for detecting and recognizing molecular species and crystalline structures. In this work, we demonstrate, by means of high-resolution reflectivity measurements, that a one-dimensional photonic crystal can sustain Bloch surface waves in the infrared spectral range from room temperature down to 10 K. To the best of our knowledge, this is the first demonstration of infrared Bloch surface waves at cryogenic temperatures. Furthermore, by exploiting the enhancement of the surface state and the high brilliance of infrared synchrotron radiation, we demonstrate that the proposed BSW-based sensor has a sensitivity on the order of 2.9 cm-1 for each nanometer-thick ice layer grown on its surface below 150 K. In conclusion, we believe that Bloch surface wave-based sensors are a valid new class of surface mode-based sensors for applications in materials science.

Optical properties of (SrMnO3)n/(LaMnO3)2n superlattices: an insulator-to-metal transition observed in the absence of disorder.

We measure the optical conductivity, σ1(ω), of (SrMnO3)n/(LaMnO3)2n superlattices (SL) for n = 1, 3, 5, and 8 and 10 < T < 400 K. Data show a T-dependent insulator to metal transition (IMT) for n ≤ 3, driven by the softening of a polaronic mid-infrared band. At n = 5 that softening is incomplete, while at the largest-period n = 8 compound the MIR band is independent of T and the SL remains insulating. One can thus first observe the IMT in a Manganite system in the absence of the disorder due to chemical doping. Unsuccessful reconstruction of the SL optical properties from those of the original bulk materials suggests that (SrMnO3)n/(LaMnO3)2n heterostructures give rise to a novel electronic state.

Normal mode calculation and infrared spectroscopy of proteins in water solution: Relationship between amide I transition dipole strength and secondary structure.

Dipole Strength (DS) of the amides has gained a renewed interest in chemical physics since it provides an important tool to disclose the on-site vibrational energy distributions. Apart from earlier experimental efforts on polypeptides, little is still known about DS in complex proteins. We accurately measured the Fourier Transform Infrared absorption spectra of nine proteins in water solution obtaining their Molar Extinction Coefficient in the amide I and II spectral region. Our results show that the amide I DS value depends on the protein secondary structure, being that of the α-rich and unstructured proteins lower by a factor of 2 than that of the ß-rich proteins. The average DS for amino acids in α and ß secondary structures confirms this finding. Normal Mode calculation and Molecular Dynamics were performed and used as tools for data analysis and interpretation. The present outcomes corroborate the hypothesis that antiparallel ß-sheet environment is more prone to delocalize the on-site CO stretching vibration through coupling mechanisms between carbonyl groups, whereas α-helix structures are energetically less stable to permit vibrational mode delocalization.

Spectral Characterization of Mid-Infrared Bloch Surface Waves Excited on a Truncated 1D Photonic Crystal.

The many fundamental roto-vibrational resonances of chemical compounds result in strong absorption lines in the mid-infrared region (λ ∼ 2-20 µm). For this reason, mid-infrared spectroscopy plays a key role in label-free sensing, in particular, for chemical recognition, but often lacks the required sensitivity to probe small numbers of molecules. In this work, we propose a vibrational sensing scheme based on Bloch surface waves (BSWs) on 1D photonic crystals to increase the sensitivity of mid-infrared sensors. We report on the design and deposition of CaF2/ZnS 1D photonic crystals. Moreover, we theoretically and experimentally demonstrate the possibility to sustain narrow σ-polarized BSW modes together with broader π-polarized modes in the range of 3-8 µm by means of a customized Fourier transform infrared spectroscopy setup. The multilayer stacks are deposited directly on CaF2 prisms, reducing the number of unnecessary interfaces when exciting in the Kretschmann-Raether configuration. Finally, we compare the performance of mid-IR sensors based on surface plasmon polaritons with the BSW-based sensor. The figures of merit found for BSWs in terms of confinement of the electromagnetic field and propagation length puts them as forefrontrunners for label-free and polarization-dependent sensing devices.

Cytochrome c aggregation: A dataset at and far from the isoelectric point.

We present SEM, ThT fluorescence and circular dichroism (CD) data of amyloidogenic aggregates of cytochrome c (cyt c).This protein is of outmost relevance in many biochemical processes, such as respiratory chain in mitochondria and cells apoptosis. The present data focus on polymorphism of the protein aggregates obtained at the isoelectric point (IP) and by changing the environmental pH above and below the IP, the protein concentration and the base. The SEM images provide evidence for a large variety of structures, depending on the pH and on protein concentration: mature amyloid fibrils and overstructured platelets are distinguishable in the aggregates below IP, and relatively high cyt c concentration, whereas inhomogeneous amyloid formations are observed above it. At pH 10, i.e. close to IP, only characteristic protein particulates at the micrometric scale are observed. SEM and Fluorescence data have been acquired in dried drops of protein solution, prepared in different bases: TRIS-HCl, at the different pH values, or NaOH (pH 13). Along with this, at relatively low cyt c concentration compact layered structures are visible below the IP, though still made of a thin fibrils reticulate, whereas above the IP, also at low cyt c concentration, granulates structures are present, merging into compact layer, alongside with platelets and mature fibers. These areas are characterized by diffuse ThT-fluorescence and typical fibrils. The loss of the predominant alpha helix secondary structure was verified by CD spectra. Besides the intrinsic scientific relevance, this data collection provides a set of images useful for spectroscopists to discriminate among different morphologic protein formations and suggests pathways for the achievement of different kinds of cytochrome c aggregates. These data are add-ons of the paper published in the International Journal of Biomacromolecules, 138 (2019) 106-115, https://doi.org/10.1016/j.ijbiomac.2019.07.060.