Gamma Irradiation Effect on Polymeric Chains of Epoxy Adhesive.

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.

Multi-length scale structural investigation of lysozyme self-assembly.

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.

Temperature Dependence of Spin-Phonon Coupling in [VO(acac)2]: A Computational and Spectroscopic Study.

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.

Pressure Effects on Water Dynamics by Time-Resolved Optical Kerr Effect.

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.

Superheating and Homogeneous Melting Dynamics of Bulk Ice.

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.

Time-domain THz spectroscopy of the characteristics of hydroxyapatite provides a signature of heating in bone tissue.

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.

Spin Dynamics and Low Energy Vibrations: Insights from Vanadyl-Based Potential Molecular Qubits.

Here we report the investigation of the magnetization dynamics of a vanadyl complex with diethyldithiocarbamate (Et2dtc-) ligands, namely [VO(Et2dtc)2] (1), in both solid-state and frozen solution. This showed an anomalous and unprecedentedly observed field dependence of the relaxation time, which was modeled with three contributions to the relaxation mechanism. The temperature dependence of the weight of the two processes dominating at low fields was found to well correlate with the low energy vibrations as determined by THz spectroscopy. This detailed experimental comparative study represents a fundamental step to understand the spin dynamics of potential molecular quantum bits, and enriches the guidelines to design molecule-based systems with enhanced quantum coherence.

Picosecond optical parametric generator and amplifier for large temperature-jump.

An optical parametric generator and amplifier producing 15 ps pulses at wavelengths tunable around 2 µm, with energies up to 15 mJ/pulse, has been realized and characterized. The output wavelength is chosen to match a vibrational combination band of water. By measuring the induced birefringence changes we prove that a single pulse is able to completely melt samples of ice in the 10⁻6 cm³ volume range, both at room pressure (263 K) and at high pressure (298 K, 1 GPa) in a sapphire anvil cell. This source opens the possibility of studying melting and freezing processes by spectroscopic probes in water or water solutions in a wide range of conditions as found in natural environments.

A comparative study on bulk and nanoconfined water by time-resolved optical Kerr effect spectroscopy.

The low frequency (nu < 500 cm(-1)) vibrational spectra of hydrated porous silica are specifically sensitive to the hydrogen bond interactions and provide a wealth of information on the structural and dynamical properties of the water contained in the pores of the matrix. We investigate systematically this spectral region for a series of Vycor porous silica samples (pore size approximately equal 4 nm) at different levels of hydration, from the dry matrix to completely filled pores. The spectra are obtained as the Fourier transforms of time-resolved heterodyne detected optical Kerr effect (HD-OKE) measurements. The comparison of these spectra with that of bulk water enables us to separately extract and analyze the spectral contributions of the first and second hydration layers, as well as that of bulk-like inner water. We conclude that the extra water entering the pores above approximately equal 10% water/silica weight ratio behaves very similarly to bulk water. At lower levels of hydration, corresponding to two complete superficial water layers or less, the H-bond bending and stretching bands, characteristic of the tetrahedral coordination of water in the bulk phase, progressively disappear: clearly in these conditions the H-bond connectivity is very different from that of liquid water. A similar behavior is observed for the structural relaxation times measured from the decay of the time-dependent HD-OKE signal. The value for the inner water is very similar to that of the bulk liquid; that of the first two water layers is definitely longer by a factor approximately equal 4. These findings should be carefully taken into account when employing pore confinement to extend towards lower temperatures the accessible temperature range of supercooled water.

Inverse freezing in molecular binary mixtures of alpha-cyclodextrin and 4-methylpyridine.

Ternary solutions of alpha-cyclodextrin (alphaCD) in 4-methylpyridine (4MP)/water mixtures solidify when heated and melt when cooled, and the crystalline solid phase exhibits a rich phase behavior as a function of temperature. In this work, we extend these earlier investigations to pure binary mixtures of alphaCD in water free 4MP, characterized via temperature and time dependent measurements of viscosity, X-ray diffraction, and infrared spectroscopy, complemented by observations of acoustic properties and small angle neutron diffraction. At high concentrations (>500 g l(-1)), these solutions enter an amorphous solid phase not only with decreasing but also with increasing temperature, before crystallizing at higher temperatures. This inverse solidification is attributed to the growth of hydrogen bonded clusters, leading to a steep increase of the viscosity with temperature.

Supercooled water relaxation dynamics probed with heterodyne transient grating experiments.

We report results from a heterodyne-detected transient grating experiment on liquid and supercooled water in a wide temperature range, from -17.5 to 90 degrees C. The measured signal covers an extremely large time window with an excellent signal-to-noise ratio that enables the investigation in a single experiment of the sound speed and attenuation, thermal diffusivity, and temperature dependence of the dielectric constant. The experimental data clearly show the effect of the density and the temperature fluctuations on the water dielectric function. In order to describe the experimental results, we introduce a comprehensive hydrodynamic model taking into account the coupled density and temperature variables and their relevance in the definition of the spontaneous and forced dielectric variations. We use this model to describe the measured signal in transient grating experiments, including the heating and the electrostrictive sources produced by the laser excitation. The fitting procedure enables the safe extraction of several dynamic properties of liquid and supercooled water: the sound velocity and its damping, the thermal diffusivity, and the ratio between the dielectric thermodynamic derivatives. The measured parameters are compared to the literature data and discussed in the complex scenario of water physics.