Quantum motion of oxygen and hydrogen in water: Atomic and total kinetic energy across melting from neutron scattering measurements.

We provide a concurrent measurement of the hydrogen and oxygen nuclear kinetic energies in the water molecule across melting at 270 K in the solid phase and 276 K in the liquid phase. Experimental values are obtained by analyzing the neutron Compton profiles of each atomic species in a deep inelastic neutron scattering experiment. The concurrent measurement of the atom kinetic energy of both hydrogen and oxygen allows the estimate of the total kinetic energy per molecule due to the motion of nuclei, specifically 35.3 ± 0.8 and 34.8 ± 0.8 kJ/mol for the solid and liquid phases, respectively. Such a small difference supports results from ab initio simulations and phenomenological models from the literature on the mechanism of competing quantum effects across the phase change. Despite the experimental uncertainties, the results are consistent with the trend from state-of-the-art computer simulations, whereby the atom and molecule kinetic energies in the liquid phase would be slightly lower than in the solid phase. Moreover, the small change of nuclear kinetic energy across melting can be used to simplify the calculation of neutron-related environmental dose in complex locations, such as high altitude or polar neutron radiation research stations where liquid water and ice are both present: for neutron energies between hundreds of meV and tens of keV, the total scattering cross section per molecule in the two phases can be considered the same, with the macroscopic cross section only depending upon the density changes of water near the melting point.

Molecular specificity in neutron imaging: the case of hydrogen adsorption in metal organic frameworks.

Neutron imaging is the technique of choice for a number of in situ and operando applications, where a high penetration power is required. White-beam neutron imaging and energy-resolved Bragg edge imaging are successful techniques, the former for the detection of specific elements characterized by strong neutron attenuation and the latter for studying crystal structures. Here we discuss the capabilities of energy-selective neutron imaging taking advantage of the incoherent and inelastic scattering interactions in hydrogenous materials, as a way to obtain molecular-specific information about the composition of a given sample. While few examples from the available literature are discussed, a worked example is presented based on new experimental data on molecular-hydrogen adsorption and conversion in the HKUST-1 metal organic framework.

Characterization of Conductive Carbon Nanotubes/Polymer Composites for Stretchable Sensors and Transducers.

The increasing interest in stretchable conductive composite materials, that can be versatile and suitable for wide-ranging application, has sparked a growing demand for studies of scalable fabrication techniques and specifically tailored geometries. Thanks to the combination of the conductivity and robustness of carbon nanotube (CNT) materials with the viscoelastic properties of polymer films, in particular their stretchability, "surface composites" made of a CNT on polymeric films are a promising way to obtain a low-cost, conductive, elastic, moldable, and patternable material. The use of polymers selected for specific applications, however, requires targeted studies to deeply understand the interface interactions between a CNT and the surface of such polymer films, and in particular the stability and durability of a CNT grafting onto the polymer itself. Here, we present an investigation of the interface properties for a selected group of polymer film substrates with different viscoelastic properties by means of a series of different and complementary experimental techniques. Specifically, we studied the interaction of a single-wall carbon nanotube (SWCNT) deposited on two couples of different polymeric substrates, each one chosen as representative of thermoplastic polymers (i.e., low-density polyethylene (LDPE) and polypropylene (PP)) and thermosetting elastomers (i.e., polyisoprene (PI) and polydimethylsiloxane (PDMS)), respectively. Our results demonstrate that the characteristics of the interface significantly differ for the two classes of polymers with a deeper penetration (up to about 100 µm) into the polymer bulk for the thermosetting substrates. Consequently, the resistance per unit length varies in different ranges, from 1-10 kΩ/cm for typical thermoplastic composite devices (30 µm thick and 2 mm wide) to 0.5-3 MΩ/cm for typical thermosetting elastomer devices (150 µm thick and 2 mm wide). For these reasons, the composites show the different mechanical and electrical responses, therefore suggesting different areas of application of the devices based on such materials.

Hydrogen Detection Limits and Instrument Sensitivity of High-Resolution Broadband Neutron Spectrometers.

The limits of detection (LOD) and quantitation (LOQ) in the mass domain, for broadband vibrational spectroscopy with neutrons on the TOSCA spectrometer at the ISIS Pulsed Neutron and Muon Source (UK), have been studied. The well-known 3σ and 10σ approaches are used through a specifically developed analytical procedure that is based on the calculation of the integrated spectral intensities in selected energy-transfer ranges, as a function of mass of standard reference materials and calibrants, such as ZrH2, 2,5-diiodothiophene, and low-density polyethylene. The analysis shows that the blank, that is, the instrument setup without the analyte, plays a critical role in the measurement performance, especially for small specimen quantities. The results point that TOSCA enables detection of 128 µmol (LODH) and quantitation of 428 µmol (LOQH) of elemental hydrogen analytes in ZrH2. The determined values for this and other standards allow for the assessment of the calibration curve design and instrument sensitivity and define a method to be used for inelastic neutron scattering spectrometers such as TOSCA, or VESPA, the new beamline under construction at the European Spallation Source in Lund (Sweden).

Changes in the hydrogen nuclear kinetic energy across the several phases of methylammonium lead tribromide.

We present an experimental investigation of methylammonium lead tribromide single crystals in the orthorhombic, tetragonal, and cubic phases based on inelastic and deep inelastic neutron scattering experiments. We show how the average hydrogen nuclear kinetic energy, mainly affected by zero-point vibrational energies, shows differences larger compared to the changes simply related to temperature effects when moving from one phase to another. In particular, the Gaussian contribution to the average nuclear kinetic energy is larger in the tetragonal phase compared to the cubic and orthorhombic ones. Moreover, we find that the vibrational densities of states of MAPbBr3 single crystals in the orthorhombic phase are compatible with previously reported results on powder samples, and that the only vibrational modes that show slightly different frequencies compared to MAPbI3 are those in the energy range between 100 and 300 cm-1, related to librational/rotational modes. As these shifts are of about 10 cm-1 and do not affect any higher-energy vibrational mode, we conclude that the zero-point energies and average nuclear kinetic energies in the two-hybrid organic/inorganic perovskites are expected to be approximately the same within a harmonic framework.

Hydrogen nuclear mean kinetic energy in water down the Mariana Trench: Competition of pressure and salinity.

The Mariana Trench is one of the most famous and extreme environments on our planet. We report experimental values of the hydrogen nuclear mean kinetic energy in water samples at the same physical and chemical conditions than in the Challenger Deep within the Mariana Trench: a pressure of 1092 bars, a temperature of 1 °C, and a salinity of 35 g of salt per kg of water. Results were obtained by deep inelastic neutron scattering at the VESUVIO spectrometer at ISIS. We find that the effect of pressure is to increase the hydrogen nuclear mean kinetic energy with respect to ambient conditions, while ions in the solution have the opposite effect. These results confirm the recent state-of-the-art simulations of the nuclear hydrogen dynamics in water. The changes in the nuclear mean kinetic energy likely correspond to different isotopic fractionation values in the Challenger Deep compared to standard sea water.

The effective isotropy of the hydrogen local potential in biphenyl and other hydrocarbons.

We present an experimental investigation of the hydrogen nuclear momentum distribution in biphenyl using deep inelastic neutron scattering. Our experimental results suggest that the local potential affecting hydrogen is both harmonic and isotropic within experimental uncertainties. This feature is interpreted as a consequence of the central limit theorem, whereby the three-dimensional momentum distribution is expected to become a purely Gaussian function as the number of independent vibrational modes in a system increases. We also performed ab initio phonon calculations on biphenyl and other saturated hydrocarbons, from methane to decane. From the results of the simulations, one can observe that the nuclear momentum distribution becomes more isotropic as the number of atoms and normal modes in the molecule increases. Moreover, the predicted theoretical anisotropy in biphenyl is clearly larger than in the experiment. The reason is that the total number of normal modes necessary to reproduce the experimental results is much larger than the number of normal modes encompassed by a single unit cell due to the presence of structural disorder and intermolecular interactions in the real crystal, as well as coupling of different normal modes. Finally, experimental data were collected, over a subset of detectors on the VESUVIO spectrometer at ISIS, with a novel setup to increase the count rate and signal-to-background ratio. We envision that such an optimized experimental setup can provide faster measurements and more stringent constraints for phonon calculations.

Neutrons for Cultural Heritage-Techniques, Sensors, and Detection.

Advances in research in Cultural Heritage see increasing application of a multidisciplinary approach and the combined use of physical and chemical characterization of artefacts that can be used to define their structure and their state of conservation, also providing valuable information in selecting the most suitable microclimatic conditions for the exhibition environment. This approach provides a platform for a synergic collaboration amongst researchers, restorers, conservators, and archaeologists. Existing state-of-the-art technologies for neutron-based methods are currently being applied to the study of objects of historical and cultural interest in several neutron-beam facilities around the world. Such techniques are non-invasive and non-destructive and are, therefore, ideal to provide structural information about artefacts, such as their composition, presence of alterations due to the environmental conditions, inclusions, structure of the bulk, manufacturing techniques, and elemental composition, which provide an overall fingerprint of the object's characteristics, thanks to the nature of the interaction of neutrons with matter. Here, we present an overview of the main neutron methods for the characterization of materials of interest in Cultural Heritage and we provide a brief introduction to the sensors and detectors that are used in this framework. We conclude with some case studies underlining the impact of these applications in different archaeological and historical contexts.

Aggregation States of Aß1-40, Aß1-42 and Aßp3-42 Amyloid Beta Peptides: A SANS Study.

Aggregation states of amyloid beta peptides for amyloid beta A ß 1 - 40 to A ß 1 - 42 and A ß p 3 - 42 are investigated through small angle neutron scattering (SANS). The knowledge of these small peptides and their aggregation state are of key importance for the comprehension of neurodegenerative diseases (e.g., Alzheimer's disease). The SANS technique allows to study the size and fractal nature of the monomers, oligomers and fibrils of the three different peptides. Results show that all the investigated peptides have monomers with a radius of gyration of the order of 10 Å, while the oligomers and fibrils display differences in size and aggregation ability, with A ß p 3 - 42 showing larger oligomers. These properties are strictly related to the toxicity of the corresponding amyloid peptide and indeed to the development of the associated disease.

Egyptian Grave Goods of Kha and Merit Studied by Neutron and Gamma Techniques.

Artifacts from the Egyptian grave goods of Kha and Merit preserved at the Museo Egizio in Turin were studied through a combination of non-destructive and non-invasive neutron and gamma techniques (namely neutron imaging, neutron diffraction and prompt gamma activation analysis). The results provide unprecedented morphological reconstructions of the inner parts of the two alabaster and metallic vases and their isotopic and phase composition, thereby extending our knowledge of the hitherto unknown content of the vases and their functions.

Probing the effects of 2D confinement on hydrogen dynamics in water and ice adsorbed in graphene oxide sponges.

We studied the single particle dynamics of water and ice adsorbed in graphene oxide (GO) sponges at T = 293 K and T = 20 K. We used Deep Inelastic Neutron Scattering (DINS) at the ISIS neutron and muon spallation source to derive the hydrogen mean kinetic energy, 〈EK〉, and momentum distribution, n(p). The goal of this work was to study the hydrogen dynamics under 2D confinement and the potential energy surface, fingerprinting the hydrogen interaction with the layered structure of the GO sponge. The observed scattering is interpreted within the framework of the impulse approximation. Samples of both water and ice adsorbed in GO show n(p) functions with almost harmonic and anisotropic line shapes and 〈EK〉 values in excess of the values found at the corresponding temperatures in the bulk. The hydrogen dynamics are discussed in the context of the interaction between the interfacial water and ice and the confining hydrophilic surface of the GO sponge.

Fluorinated borono-phenylalanine for optimizing BNCT: Enhancing boron absorption against hydrogen scattering for thermal neutrons.

BACKGROUND: Boron-containing compounds, such as 4-borono-phenylalanine (BPA) are used as drugs for cancer treatment in the framework of Boron Neutron Capture Therapy (BNCT). Neutron irradiation of boron-rich compounds delivered to cancer cells triggers nuclear reactions that destroy cancer cells. PURPOSE: We provide a modeling of the thermal neutron cross section of BPA, a drug used in Boron Neutron Capture Therapy (BNCT), to quantify the competing contributions of boron absorption against hydrogen scattering, for optimizing BNCT by minimizing the latter. METHODS: We perform the experimental determination of the total neutron scattering cross section of BPA at thermal and epithermal neutron energies using neutron transmission measurements. We isolate the contribution related to the incoherent scattering by hydrogen atoms as a function of the neutron energy by means of the Average Functional Group Approximation, and we calculate the probability for a neutron of being absorbed as a function of the neutron energy both for BPA and for its variants where either one or all four aromatic hydrogen atoms are substituted by 19 F, and both for the samples with natural occurrence or enriched concentration of 10 B. RESULTS: While referring to the already available literature for in vivo use of fluorinated BPA, we show that fluorine-rich variants of BPA increase the probability of neutrons being captured by the molecule. As the higher absorption efficiency of fluorinated BPA does not depend on whether the molecule is used in vivo or not, our results are promising for the higher efficiency of the boron neutron capture treatment. CONCLUSIONS: Our results suggest a new advantage using fluorinated compounds for BNCT, in their optimized interaction with neutrons, in addition to their already known capability to be used for monitoring and pharmacokinetics studies using 19 F-Nuclear Magnetic Resonance or in 18 F-Positron Emission Tomography.

The quantum nature of the OH stretching mode in ice and water probed by neutron scattering experiments.

The OH stretching vibrational spectrum of water was measured in a wide range of temperatures across the triple point, 269 K OH, were determined for the first time within the framework of a harmonic description of the proton dynamics. We found that in the liquid the value of OH is nearly constant as a function of T, indicating that quantum effects on the OH stretching frequency are weakly dependent on temperature. In the case of ice, ab initio electronic structure calculations, using non-local van der Waals functionals, provided OH values in agreement with INS experiments. We also found that the ratio of the stretching (OH) to the total (exp) kinetic energy, obtained from the present measurements, increases in going from ice, where hydrogen bonding is the strongest, to the liquid at ambient conditions and then to the vapour phase, where hydrogen bonding is the weakest. The same ratio was also derived from the combination of previous deep inelastic neutron scattering data, which does not rely upon the harmonic approximation, and the present measurements. We found that the ratio of stretching to the total kinetic energy shows a minimum in the metastable liquid phase. This finding suggests that the strength of intermolecular interactions increases in the supercooled phase, with respect to that in ice, contrary to the accepted view that supercooled water exhibits weaker hydrogen bonding than ice.

Interaction of single water molecules with silanols in mesoporous silica.

Deep Inelastic Neutron Scattering measurements of water confined in mesoporous silica have been carried out. The experiment has been performed at room temperature on dry and on hydrated samples in order to investigate the interaction between the protons and the silanol groups of the confining surface. With this aim we could control the hydration of the pores in such a way as to adsorb 3.0 water molecules per nm(2), corresponding to a 1 to 1 ratio with the silanol groups of the surface. DINS measurements directly measure the mean kinetic energy and the momentum distribution of the protons. A detailed analysis of the hydrated sample has been performed in order to separate the contributions of the protons in the system, allowing us to determine the arrangement of water molecules on the silanol groups. We find that the hydrogen bond of the water proton with the oxygen of the silanol group is much stronger than the hydrogen bonds of bulk water.

Thermal neutron cross sections of amino acids from average contributions of functional groups.

The experimental thermal neutron cross sections of the 20 proteinogenic amino acids have been measured over the incident-neutron energy range spanning from 1 meV to 10 keV and data have been interpreted using the multi-phonon expansion based on first-principles calculations. The scattering cross section, dominated by the incoherent inelastic contribution from the hydrogen atoms, can be rationalised in terms of the average contributions of different functional groups, thus neglecting their correlation. These results can be used for modelling the total neutron cross sections of complex organic systems like proteins, muscles, or human tissues from a limited number of starting input functions. This simplification is of crucial importance for fine-tuning of transport simulations used in medical applications, including boron neutron capture therapy as well as secondary neutrons-emission induced during proton therapy. Moreover, the parametrized neutron cross sections allow a better treatment of neutron scattering experiments, providing detailed sample self-attenuation corrections for a variety of biological and soft-matter systems.

Looking for Minor Phenolic Compounds in Extra Virgin Olive Oils Using Neutron and Raman Spectroscopies.

Extra virgin olive oil (EVOO) is defined as a functional food as it contains numerous phenolic components with well-recognized health-beneficial properties, such as high antioxidant and anti-inflammatory capacity. These characteristics depend on their structural/conformational behavior, which is largely determined by intra- and intermolecular H-bond interactions. While the vibrational dynamics of isolated compounds have been studied in a number of recent investigations, their signal in a real-life sample of EVOO is overwhelmed by the major constituent acids. Here, we provide a full characterization of the vibrational spectroscopic signal from commercially available EVOO samples using Inelastic Neutron Scattering (INS) and Raman spectroscopies. The spectra are dominated by CH2 vibrations, especially at about 750 cm-1 and 1300 cm-1. By comparison with the spectra from hydroxytyrosol and other minor phenolic compounds, we show that the best regions in which to look for the structure-activity information related to the minor polar compounds is at 675 and 1200 cm-1 for hydroxytyrosol, and around 450 cm-1 for all minor polar compounds used as reference, especially if a selectively deuterated sample is available. The regional origin of the EVOO samples investigated appears to be related to the different amount of phenolic esters versus acids as reflected by the relative intensities of the peaks at 1655 and 1747 cm-1.

A Python Algorithm to Analyze Inelastic Neutron Scattering Spectra Based on the y-Scale Formalism.

This paper presents a Python-based algorithm, named INSCorNorm, to correct the inelastic neutron scattering (INS) spectra for both sample and container self-shielding and to normalize the experimental spectral intensity to an absolute physical scale (barn/energy unit) facilitating the comparison with computer simulations and interpretation. The algorithm is benchmarked against INS measurements of ZrH2 performed on the TOSCA spectrometer at the ISIS Facility. We also apply the algorithm to the INS spectra from l-lysine, a system of broad interest in biology and medicine, and we discuss how corrected INS data provide an experimental benchmark for theoretical calculations of nuclear anisotropic displacement parameters in molecular systems. The total neutron sample cross section to use for the self-shielding corrections is discussed, as well as the best approach to derive experimentally the cross section at the VESUVIO spectrometer, together with the experimental value of the hydrogen nuclear mean kinetic energy, ⟨Ek⟩. The algorithm is made available to the neutron user community within the MANTID software.

Hydrogen Dynamics in Supercritical Water Probed by Neutron Scattering and Computer Simulations.

In this work, an investigation of supercritical water is presented combining inelastic and deep inelastic neutron scattering experiments and molecular dynamics simulations based on a machine-learned potential of ab initio quality. The local hydrogen dynamics is investigated at 250 bar and in the temperature range of 553-823 K, covering the evolution from subcritical liquid to supercritical gas-like water. The evolution of libration, bending, and stretching motions in the vibrational density of states is studied, analyzing the spectral features by a mode decomposition. Moreover, the hydrogen nuclear momentum distribution is measured, and its anisotropy is probed experimentally. It is shown that hydrogen bonds survive up to the higher temperatures investigated, and we discuss our results in the framework of the coupling between intramolecular modes and intermolecular librations. Results show that the local potential affecting hydrogen becomes less anisotropic within the molecular plane in the supercritical phase, and we attribute this result to the presence of more distorted hydrogen bonds.

Carbon Nanotube-Based Stretchable Hybrid Material Film for Electronic Devices and Applications.

To meet the increasing demand, for stretchable conductive materials in a wide range of applications, innovative conductors based on single wall carbon nanotubes (SWCNT) self-grafted on different polymer films, are assembled. Aiming at a simple technology for flexible and stretchable electronic devices, and contrary to what commonly reported for carbon nanotubes (CNT), no chemical functionalization of SWCNT is necessary for stable grafting onto several polymeric surfaces. The novelty and functionality of our composite materials stand in the synergy among the intrinsic biocompatibility of CNT, a fully inert material, their electrical conductivity, and the stretchable-viscoelastic properties of the polymer-nanotube bundles composites. Electrical characterization of both unstretched and strongly stretched planar film conductors is provided, demonstrating the use of this new composite material for technological application. Also, an insight into the mechanisms of strong adhesion to the polymer is obtained by scanning electron microscopy (SEM) of the surface composite. As an example of technological application of such stretchable circuitry, the electrical functionality of a carbon nanotube-based six-sensor (electrode) grid is used to record subdural electrocorticograms in freely-moving laboratory rats over approximately three months.

Chronic neural interfacing with cerebral cortex using single-walled carbon nanotube-polymer grids.

OBJECTIVE: The development of electrode arrays able to reliably record brain electrical activity is a critical issue in brain machine interface (BMI) technology. In the present study we undertook a comprehensive physico-chemical, physiological, histological and immunohistochemical characterization of new single-walled carbon nanotubes (SWCNT)-based electrode arrays grafted onto medium-density polyethylene (MD-PE) films. APPROACH: The long-term electrical stability, flexibility, and biocompatibility of the SWCNT arrays were investigated in vivo in laboratory rats by two-months recording and analysis of subdural electrocorticogram (ECoG). Ex-vivo characterization of a thin flexible and single probe SWCNT/polymer electrode is also provided. MAIN RESULTS: The SWCNT arrays were able to capture high quality and very stable ECoG signals across 8 weeks. The histological and immunohistochemical analyses demonstrated that SWCNT arrays show promising biocompatibility properties and may be used in chronic conditions. The SWCNT-based arrays are flexible and stretchable, providing low electrode-tissue impedance, and, therefore, high compliance with the irregular topography of the cortical surface. Finally, reliable evoked synaptic local field potentials in rat brain slices were recorded using a special SWCNT-polymer-based flexible electrode. SIGNIFICANCE: The results demonstrate that the SWCNT arrays grafted in MD-PE are suitable for manufacturing flexible devices for subdural ECoG recording and might represent promising candidates for long-term neural implants for epilepsy monitoring or neuroprosthetic BMI.