Room-temperature strong coupling in organic microcavities is usually achieved by combining high-quality optical resonators with highly ordered excitonic media, a requirement that limits scalability and processing flexibility. Here we show that this constraint can be relaxed by using molecular aggregation as a design parameter rather than treating it as a parasitic effect. We realize solution-processed Rhodamine 6G-poly(vinyl alcohol) films embedded in low-quality-factor silver Fabry-Perot microcavities and demonstrate clear angle-resolved anticrossing with coupling energies up to 324 meV despite the large optical losses of the metallic mirrors. A two-exciton coupled-oscillator model shows that the relative weight of these species controls the collective coupling strength and can be tuned through dye loading and spin-coating conditions. In contrast, angle-resolved photoluminescence is dominated by a broad, red-shifted lower-polariton emission, consistent with relaxation through excimer-like states formed in densely packed molecular domains. These results identify molecular aggregation as a practical design lever for loss-tolerant strong coupling in wet-processed metallic cavities and suggest that ground-state aggregates and excited-state excimer-like species play distinct roles in polariton formation and emission.

We propose a time-resolved optical Kerr effect study of the structural and vibrational dynamics of the hydration water surrounding the lysozyme on a very fast time scale. Measurements as a function of lysozyme concentration make it possible to distinguish the hydration water contribution from that of both the bulk water and the protein. Our results provide experimental evidence of the existence of two structural dynamics of hydration water, associated with a hydrogen bond exchange relaxation process and with the reorganization of water molecules induced by protein structural fluctuations. Likewise, we evaluated the vibrational dynamics of the water hydration layer at subpicosecond time scales. Our measurements of hydration water properties reveal the presence of a crossover point at a specific protein concentration. This crossover marks the transition between two clustering regimes with distinct hydration characteristics and establishes a possible threshold for protein crowding.

The study of materials for space exploration is one of the most interesting targets of international space agencies. An essential tool for realizing light junctions is epoxy adhesive (EA), which provides an elastic and robust material with a complex mesh of polymeric chains and crosslinks. In this work, a study of the structural and chemical modification of a commercial two-part flexible EA (3M™ Scotch-Weld™ EC-2216 B/A Gray), induced by 60Co gamma radiation, is presented. Combining different spectroscopic techniques, such as the spectroscopic Fourier transform infrared spectroscopy (FTIR), the THz time-domain spectroscopy (TDS), and the electron paramagnetic resonance (EPR), a characterization of the EA response in different regions of the electromagnetic spectrum is performed, providing valuable information about the structural and chemical properties of the polymers before and after irradiation. A simultaneous dissociation of polymeric chain and crosslinking formation is observed.The polymer is not subject to structural modification at an absorbed dose of 10 kGy, in which only transient free radicals are observed. Differently, between 100 and 500 kGy, a gradual chemical degradation of the samples is observed together with a broad and long-living EPR signal appearance. This study also provides a microscopic characterization of the material useful for the mechanism evaluation of system degradation.

In recent years, the use of techniques based on electromagnetic radiation as an investigative tool in the agri-food industry has grown considerably, and between them, the application of imaging and THz spectroscopy has gained significance in the field of food quality control. This study presents the development of an experimental setup operating in transmission mode within the frequency range of 18 to 40 GHz, which was specifically designed for assessing various quality parameters of hazelnuts. The THz measurements were conducted to distinguish between healthy and rotten hazelnut samples. Two different data analysis techniques were employed and compared: a traditional approach based on data matrix manipulation and curve fitting for parameter extrapolation, and the utilization of a Self-Organizing Map (SOM), for which we use a neural network commonly known as the Kohonen neural network, which is recognized for its efficacy in analyzing THz measurement data. The classification of hazelnuts based on their quality was performed using these techniques. The results obtained from the comparative analysis of coding efforts, analysis times, and outcomes shed light on the potential applications of each method. The findings demonstrate that THz spectroscopy is an effective technique for quality assessment in hazelnuts, and this research serves to clarify the suitability of each analysis technique.

Wood is a hygroscopic material that is subject to phenomena of water exchange with the external environment.These exchanges can cause dimensional variations and cracks to appear on a macroscopic level.In recent years, the use of terahertz technologies in the field of diagnostics applied to cultural heritage has increased considerably.One of the most important characteristics of terahertz radiation is its sensitivity to water content; this polar liquid strongly absorbs and reflects this radiation.The subject of this study will be the detection of moisture in pine wood samples using a 97 GHz terahertz imaging system.

An experimental setup operating in transmission mode in the frequency range between 18 and 40 GHz is described. This study shows how the system is able to distinguish healthy and rotten hazelnuts. In addition, a Self-Organizing Map (SOM) trained with the Kohonen algorithm was used to classify the hazelnuts according to their quality.

In recent years, the concept of smart agriculture has entered our collective daily routine by radically modifying the methods by which crop monitoring was previously carried out. More precisely, the term smart farming focuses its attention on the use technologies already present on the market like, sensors (multispectral, hyperspectral, thermal and terahertz sensors), WNS (wireless sensor network) and drones capable to reduce the human work in the fields, optimizing at the same time the quantity and quality of the products limiting the use of resources, as water, fertilizers, pesticides and herbicides. Recently, one of the most important problem in the field of precision farming is the availability of water; unfortunately, this factor becomes more critical from year to year. To resolve this problem, the first step is to reduce consumption and rationalize the use of water by adjusting the water supply to the needs of the systems in order to increase its yield while saving money. In this respect, the development of non-destructive techniques operating in the THz spectral region has allowed to monitor in real time the water content present in leaves and plants. In fact, due to the strong water absorption and reflection in this spectral region, this feature can be exploited to detect the water content of leaves and plants helping us to intervene promptly in cases where the plant needs water, avoiding so does water stress, but above all trying to use our primary resource adequately by reducing waste. About this, Imaging and Time-Domain Spectroscopy (THz-TDS) techniques have been applied to monitor soil conditions, drought stress and presence of pathogens on the plants. In this review, we focus our attention on the latest research carried out on monitoring the water content present in leaves through THz technologies. Moreover, we pose particular attention in the description of our system set composed by a 97 GHz transmitter-receiver able to analyze the spatial distribution of the water inside a leaf.

Reactive amyloid oligomers are responsible for cytotoxicity in amyloid pathologies and because of their unstable nature characterizing their behavior is a challenge. The physics governing the self-assembly of proteins in crowded conditions is extremely complex and its comprehension, despite its paramount relevance to understanding molecular mechanisms inside cells and optimizing pharmaceutical processes, remains inconclusive. Here, we focus on the amyloid oligomerization process in self-crowded lysozyme aqueous solutions in acidic conditions. We reveal that the amyloid oligomers form at high protein concentration and low pH. Through multi-length scale spectroscopic investigations, we find that amyloid oligomers can further interconnect with each other by weak and non-specific interactions forming an extended network that leads to the percolation of the whole system. Our multi-length scale structural analysis follows the thermal history of amyloid oligomers from different perspectives and highlights the impact of hierarchical self-assembly of biological macromolecules on functional properties.

Molecular electronic spins are good candidates as qubits since they are characterized by a large tunability of their electronic and magnetic properties through a rational chemical design. Coordination compounds of light transition metals are promising systems for spin-based quantum information technologies, thanks to their long spin coherence times up to room temperature. Our work aims at presenting an in-depth study on how the spin-phonon coupling in vanadyl-acetylacetonate, [VO(acac)2], can change as a function of temperature using terahertz time-domain spectroscopy and density functional theory (DFT) calculations. Powder THz spectra were recorded between 10 and 300 K. The temperature dependence of vibrational frequencies was then accounted for in the periodic DFT calculations using unit-cell parameters measured at two different temperatures and the optimized ones, as usually reported in the literature. In this way, it was possible to calculate the observed THz anharmonic frequency shift with high accuracy. The overall differences in the spin-phonon coupling magnitudes as a function of temperature were also highlighted showing that the computed trends have to be ascribed to the anisotropic variation of cell parameters.

The presence of ions induces perturbations in the water network, these structural and dynamic modifications can extent over space scales overcoming the local solvation shell: aqueous solutions of sodium perchlorate (NaClO4) are characterized by extended phenomena of structure breaking of the solvent network. The aim of the present work is the experimental investigation of the interplay between the local structural modifications induced by the perchlorate ions and the collective dynamical properties of the solvent. Ultrafast Optical Kerr Effect (OKE) and time resolved infrared absorption are the experimental techniques adopted: OKE is mostly sensitive to the collective properties of the sample, while transient IR provides access to local properties of the solvent. Classical Molecular Dynamics (MD) simulations support the analysis of the experimental results. All experiments and simulations are performed at room temperature, varying the concentrations (0-6 M) and varying the applied pressure (10(-4)-1.3 GPa). Experiments and computer simulations confirm that pressure and concentration have convergent effects on the water dynamics, due to the analogous modification of the short-range liquid structure that cancel some dynamical anomalies typical of pure water. Both local and collective dynamic observables point to structural properties as responsible for their peculiar pressure and concentration dependence. (C) 2021 Elsevier B.V. All rights reserved.

Despite water being the most common and most widely studied substance in the world, it still presents unknown aspects. In particular, water shows several thermodynamic and dynamical anomalies in the liquid and supercooled metastable phases, and the natures of these phases are still hotly debated. Here, we report measurements of water using the optical Kerr effect as a function of pressure along two isotherms, at 273 K from 0.1 to 750 MPa and at 297 K from 0.1 to 1350 MPa, reaching the supercooled metastable phase. The structural relaxation and the low frequency vibrational dynamics of water show a peculiar pressure dependence similar to that of other dynamical properties. The data analysis suggests the presence in the water phase diagram of a crossover area that divides two regions characterized by different dynamic regimes, which appear to be related to two liquid forms, one dominated by the high density water and the other by the low density water.

Super-resolution microscopy refers to a powerful set of imaging techniques that overcome the diffraction limit. Some of these techniques, the importance of which was recognized by the 2014 Nobel Prize for chemistry, are based on the concept of image reconstruction by spatially sparse sampling. Here, we introduce the concept of super-resolution spectroscopy based on sparse sampling in the frequency domain, and show that this can be naturally achieved using a random laser source. In its chaotic regime, the emission spectrum of a random laser features sharp spikes at uncorrelated frequencies that are sparsely distributed over the emission bandwidth. These narrow lasing modes probe stochastically the spectral response of a sample, allowing it to be reconstructed with a resolution exceeding that of the spectrometer. We envision that the proposed technique will inspire a new generation of simple, cheap, high-resolution spectroscopy tools with a reduced footprint. Spectral super-resolution spectroscopy is realized by exploiting a random laser that chaotically produces sharply spiked spectral lines, representing a new generation of simple, compact and cost-effective spectroscopy tools.

The nucleation processes are still today between the more intriguing problems of the condensed [...]

The homogeneous melting of a crystal is a complex process that involves the formation of transient states at a temperature higher than the thermodynamic melting point[1]. The characteristics of the transient states and the duration time they exist are peculiar of the type of crystal (molecular, covalent, hydrogen-bonded, ionic, metallic, etc.) and they are far to be well understood even for simple systems[2]. We conceived a new kind of time resolved experiment to study, by means of transient infrared spectroscopy with high temporal resolution, the entire dynamics of the superheating and melting process, ranging from few tens of picoseconds, up to the millisecond time regime, for samples compressed in sapphire anvil cells. We characterized the time constant associated to homogeneous melting of a molecular and H-bonded crystal of paramount importance: water ice (Ih). We found an incredibly long-lasting metastable superheated state in which ice persists for tens of nanoseconds at a temperature higher than the thermodynamic melting point, without undergoing to melt. This is preliminary to the study of the melting dynamics of the high pressure phases of water (III, V, VI, VII) and binary systems like clathrate hydrates, which aims to understand the effect of density and molecular arrangement on the characteristic lifetimes of the melting itself, and the metastable transient states involved in the melting process.

The time-resolved spectroscopy based on polarization effects represents one of the most sensitive techniques for studying dynamical phenomena in condensed matter. The optical Kerr effect performed with ultra-short laser pulses enables a unique investigation of dynamic processes covering a wide time range, typically from few femtoseconds up to many nanoseconds. This spectroscopic tool is particularly well suited for the measurement of relaxation patterns in complex liquids where several dynamic phenomena, taking place on different time scales, are present. In this chapter we introduce the optical Kerr effect principles, the experimental procedure, and some results from measurements in a number of different complex liquids.

In this work, we studied the propagation of ultrasonic waves of lysozyme solutions characterized by different degrees of aggregation and networking. The experimental investigation was performed by means of the transient grating (TG) spectroscopy as a function of temperature, which enabled measurement of the ultrasonic acoustic proprieties over a wide time window, ranging from nanoseconds to milliseconds. The fitting of the measured TG signal allowed the extraction of several dynamic properties, here we focused on the speed and the damping rate of sound. The temperature variation induced a series of processes in the lysozyme solutions: Protein folding-unfolding, aggregation and sol–gel transition. Our TG investigation showed how these self-assembling phenomena modulate the sound propagation, affecting both the velocity and the damping rate of the ultrasonic waves. In particular, the damping of ultrasonic acoustic waves proved to be a dynamic property very sensitive to the protein conformational rearrangements and aggregation processes.

Homogeneous melting of crystals is a complex multistep process involving the formation of transient states at temperatures considerably higher than the melting point. The nature and persistence of these metastable structures are intimately connected to the melting process, and a precise definition of the temporal boundaries of these phenomena is not yet available. We set up a specifically designed experiment to probe by transient infrared absorption spectroscopy the entire dynamics, ranging from tens of picoseconds to microseconds, of superheating and melting of an ice crystal. In spite of a large excess of energy provided, only about 30% of the micrometric crystal liquefies in the first 20-25 ns because of the long persistence of the superheated metastable phase that extends for more than 100 ns. This behavior is ascribed to the population of low-energy states that trap a large amount of energy, favoring the formation of a metastable, likely plastic, ice phase.

Because of the importance of bone in the biomedical, forensic and archaeological contexts, new investigation techniques are constantly required to better characterize bone ultrastructure. In the present paper, we provide an extended investigation of the vibrational features of bone tissue in the 0.1-3 THz frequency range by time-domain THz spectroscopy. Their assignment is supported by a combination of X-ray diffraction and DFT-normal modes calculations. We investigate the effect of heating on bone tissue and synthetic calcium-phosphates compounds with close structure and composition to bone mineral, including stoichiometric and non-stoichiometric hydroxyapatite (HA), tricalcium phosphate, calcium pyrophosphate and tetracalcium phosphate. We thus demonstrate that the narrow vibrational mode at 2.1 THz in bone samples exposed to thermal treatment above 750 °C arises from a lattice mode of stoichiometric HA. This feature is also observed in the other synthetic compounds, although weaker or broader, but is completely smeared out in the non-stoichiometric HA, close to natural bone mineral composition, or in synthetic poorly crystalline HA powder. The THz spectral range therefore provides a clear signature of the crystalline state of the investigated bone tissue and could, therefore be used to monitor or identify structural transitions occurring in bone upon heating.

THz time domain spectroscopy is a powerful technique enabling the investigation of different materials in the far-infrared frequency range. Even if nowadays this technique is well established, its application to very thin films remains particularly difficult. We investigated the utilization of THz spectroscopy on samples of micrometric thickness with the aim to disentangle multiple reflections and to measure with high accuracy the absolute values of the material parameters. We implemented an experimental and data analysis procedure that can be applied to free-standing single-layers or multi-layers samples. Specifically, we report on the experimental investigation by THz time domain spectroscopy of two samples: a test sample made of two layers of known thickness and materials; and a second sample, that is of a great interest for cultural heritage studies, made of a thin film of ink layered on a thicker support. Moreover, we describe in details the data analysis and fitting procedures needed to extract the material parameters from the experimental results.