Low-oxidation-state Ru sites stabilized in carbon-doped RuO2 with low-temperature CO2 activation to yield methane.

The generation of methane fuel using surplus renewable energy with CO2 as the carbon source enables both the decarbonization and substitution of fossil fuel feedstocks. However, high temperatures are usually required for the efficient activation of CO2. Here we present a solid catalyst synthesized using a mild, green hydrothermal synthesis that involves interstitial carbon doped into ruthenium oxide, which enables the stabilization of Ru cations in a low oxidation state and a ruthenium oxycarbonate phase to form. The catalyst shows an activity and selectivity for the conversion of CO2 into methane at lower temperatures than those of conventional catalysts, with an excellent long-term stability. Furthermore, this catalyst is able to operate under intermittent power supply conditions, which couples very well with electricity production systems based on renewable energies. The structure of the catalyst and the nature of the ruthenium species were acutely characterized by combining advanced imaging and spectroscopic tools at the macro and atomic scales, which highlighted the low-oxidation-state Ru sites (Run+, 0 < n < 4) as responsible for the high catalytic activity. This catalyst suggests alternative perspectives for materials design using interstitial dopants.

An Eutectic Mixture in the Tetrabutylammonium Bromide-Octanol System: Macroscopic and Microscopic Points of View.

An eutectic mixture of tetrabutylammonium bromide and octanol in the molar ratio 1-10 exhibited a melting point of -17 °C. This system was investigated by means of infrared spectroscopy, in the liquid and in the solid state. Classical molecular dynamics was performed to study the fine details of the hydrogen bond interactions established in the mixture. Both octanol and the mixtures displayed an almost featureless far-infrared spectrum in the liquid state but it becomes highly structured in the solid phase. DFT calculations suggest that new vibrational modes appearing in the mixture at low temperatures may be related to the population of the higher energy conformers of the alcohol. Mid-infrared spectroscopy measurements evidenced no shift of the CH stretching bands in the mixture compared to the starting materials, while the OH stretching are blue shifted by a few cm-1. Consistently, molecular dynamics provides a picture of the mixture in which part of the hydrogen bonds (HB) of pure octanol is replaced by weaker HB formed with the Br anion. Due to these interactions the ionic couple becomes more separated. In agreement with this model, the lengths of all HB are much larger than those observed in mixtures containing acids reported in previous studies.

Stripping away ion hydration shells in electrical double-layer formation: Water networks matter.

The double layer at the solid/electrolyte interface is a key concept in electrochemistry. Here, we present an experimental study combined with simulations, which provides a molecular picture of the double-layer formation under applied voltage. By THz spectroscopy we are able to follow the stripping away of the cation/anion hydration shells for an NaCl electrolyte at the Au surface when decreasing/increasing the bias potential. While Na+ is attracted toward the electrode at the smallest applied negative potentials, stripping of the Cl- hydration shell is observed only at higher potential values. These phenomena are directly measured by THz spectroscopy with ultrabright synchrotron light as a source and rationalized by accompanying molecular dynamics simulations and electronic-structure calculations.

Restriction site-associated DNA sequencing technologies as an alternative to low-density SNP chips for genomic selection: a simulation study in layer chickens.

BACKGROUND: To reduce the cost of genomic selection, a low-density (LD) single nucleotide polymorphism (SNP) chip can be used in combination with imputation for genotyping selection candidates instead of using a high-density (HD) SNP chip. Next-generation sequencing (NGS) techniques have been increasingly used in livestock species but remain expensive for routine use for genomic selection. An alternative and cost-efficient solution is to use restriction site-associated DNA sequencing (RADseq) techniques to sequence only a fraction of the genome using restriction enzymes. From this perspective, use of RADseq techniques followed by an imputation step on HD chip as alternatives to LD chips for genomic selection was studied in a pure layer line. RESULTS: Genome reduction and sequencing fragments were identified on reference genome using four restriction enzymes (EcoRI, TaqI, AvaII and PstI) and a double-digest RADseq (ddRADseq) method (TaqI-PstI). The SNPs contained in these fragments were detected from the 20X sequence data of the individuals in our population. Imputation accuracy on HD chip with these genotypes was assessed as the mean correlation between true and imputed genotypes. Several production traits were evaluated using single-step GBLUP methodology. The impact of imputation errors on the ranking of the selection candidates was assessed by comparing a genomic evaluation based on ancestry using true HD or imputed HD genotyping. The relative accuracy of genomic estimated breeding values (GEBVs) was investigated by considering the GEBVs estimated on offspring as a reference. With AvaII or PstI and ddRADseq with TaqI and PstI, more than 10 K SNPs were detected in common with the HD SNP chip, resulting in an imputation accuracy greater than 0.97. The impact of imputation errors on genomic evaluation of the breeders was reduced, with a Spearman correlation greater than 0.99. Finally, the relative accuracy of GEBVs was equivalent. CONCLUSIONS: RADseq approaches can be interesting alternatives to low-density SNP chips for genomic selection. With more than 10 K SNPs in common with the SNPs of the HD SNP chip, good imputation and genomic evaluation results can be obtained. However, with real data, heterogeneity between individuals with missing data must be considered.

Nest preference and laying duration traits to select against floor eggs in laying hens.

BACKGROUND: Floor eggs, which are defined as eggs that hens lay off-nest, are a major issue in cage-free layer poultry systems. They create additional work for farmers because they must be collected by hand. They are also usually soiled or broken, which results in economic losses. Nonetheless, knowledge about the genetics of nesting behavior is limited. The aim of this study was to estimate genetic parameters for traits related to nest preference for laying and to time spent in the nests used for laying (laying duration). METHODS: Two pure lines of laying hens were studied: 927 Rhode Island Red and 980 White Leghorn. Electronic nests were used to record the nesting behavior of these hens in floor pens from 24 to 64 weeks of age. Nest preference was studied based on the mean distance between nests used for laying and the percentage of nests used for laying. Laying duration was studied based on mean laying duration, mean duration in the nest before laying, and mean duration in the nest after laying. Genetic parameters were estimated for each line using a restricted maximum-likelihood method applied to a pedigree-based multi-trait animal model. RESULTS: Estimates of genetic parameters were similar for the two lines. Estimates of heritability ranged from 0.18 to 0.37 for nest preference traits and from 0.54 to 0.70 for laying duration traits. Estimates of genetic correlations of these traits with clutch number or mean oviposition time were favorable. Positive genetic correlations were estimated between nest preference and laying rate in the nests or nest acceptance for laying (+ 0.06 to + 0.37). CONCLUSIONS: These results show that genetics influences traits related to nest preference and laying duration. Selecting hens that have no preference for particular nests and spend little time laying in the nests could help optimize nest use, reduce their occupation rate, and thus decrease the incidence of floor eggs in cage-free systems. Genetic correlations of these traits with other traits of interest related to hen welfare and egg quality have yet to be estimated.

Aqueous TMAO solution under high hydrostatic pressure.

Trimethylamine N-oxide (TMAO) is a well known osmolyte in nature, which is used by deep sea fish to stabilize proteins against High Hydrostatic Pressure (HHP). We present a combined ab initio molecular dynamics, force field molecular dynamics, and THz absorption study of TMAO in water up to 12 kbar to decipher its solvation properties upon extreme compression. On the hydrophilic oxygen side of TMAO, AIMD simulations at 1 bar and 10 kbar predict a change of the coordination number from a dominating TMAO·(H2O)3 complex at ambient conditions towards an increased population of a TMAO·(H2O)4 complex at HHP conditions. This increase of the TMAO-oxygen coordination number goes in line with a weakening of the local hydrogen bond network, spectroscopic shifts and intensity changes of the corresponding intermolecular THz bands. Using a pressure-dependent HHP force field, FFMD simulations predict a significant increase of hydrophobic hydration from 1 bar up to 4-5 kbar, which levels off at higher pressures up to 10 kbar. THz spectroscopic data reveal two important pressure regimes with spectroscopic inflection points of the dominant intermolecular modes: The first regime (1.5-2 kbar) is barely recognizable in the simulation data. However, it relates well with the observation that the apparent molar volume of solvated TMAO is nearly constant in the biologically relevant pressure range up to 1 kbar as found in the deepest habitats on Earth in the ocean. The second inflection point around 4-5 kbar is related to the amount of hydrophobic hydration as predicted by the FFMD simulations. In particular, the blueshift of the intramolecular CNC bending mode of TMAO at about 390 cm-1 is the spectroscopic signature of increasingly pronounced pressure-induced changes in the solvation shell of TMAO. Thus, the CNC bend can serve as local pressure sensor in the multi-kbar pressure regime.

Evidence of the CH···O HydrogenBonding in Imidazolium-Based Ionic Liquids from Far-Infrared Spectroscopy Measurements and DFT Calculations.

Knowledge of all the intermolecular forces occurring in ionic liquids (ILs) is essential to master their properties. Aiming at investigating the weaker hydrogen bonding in aprotic liquids, the present work combined computational study and far-infrared spectroscopy on four imidazolium-based ILs with different anions. The DFT calculations of the ionic couples, using the ωB97X-D functional and considering both the empirical dispersion corrections and the presence of a polar solvent, show that, for all samples, the lowest energy configurations of the ion pair present H atoms, directly bound to C atoms of the cation and close to O atoms of the anion, capable of creating moderate to weak hydrogen bonding with anions. For the liquids containing anions of higher bonding ability, the absorption curves generated from the calculated vibrational frequencies and intensities show absorption bands between 100 and 125 cm-1 corresponding to the stretching of the hydrogen bond. These indications are in complete agreement with the presently reported temperature dependence of the far-infrared spectrum, where the stretching modes of the hydrogen bonding are detected only for samples presenting a moderate interaction and become particularly prominent at low temperatures. Moreover, from the analysis of the infrared spectra, the occurrence of various phase transitions as a function of temperature was detected, and the difference in the average energy between the H-bonded and the dispersion-governed molecular configurations was evaluated.

Reliability of genomic evaluation for egg quality traits in layers.

BACKGROUND: Genomic evaluation, based on the use of thousands of genetic markers in addition to pedigree and phenotype information, has become the standard evaluation methodology in dairy cattle breeding programmes over the past several years. Despite the many differences between dairy cattle breeding and poultry breeding, genomic selection seems very promising for the avian sector, and studies are currently being conducted to optimize avian selection schemes. In this optimization perspective, one of the key parameters is to properly predict the accuracy of genomic evaluation in pure line layers. RESULTS: It was observed that genomic evaluation, whether performed on males or females, always proved more accurate than genetic evaluation. The gain was higher when phenotypic information was narrowed, and an augmentation of the size of the reference population led to an increase in accuracy prediction with regard to genomic evaluation. By taking into account the increase of selection intensity and the decrease of the generation interval induced by genomic selection, the expected annual genetic gain would be higher with ancestry-based genomic evaluation of male candidates than with genetic evaluation based on collaterals. This advantage of genomic selection over genetic selection requires more detailed further study for female candidates. CONCLUSIONS: In conclusion, in the population studied, the genomic evaluation of egg quality traits of breeding birds at birth seems to be a promising strategy, at least for the selection of males.

Atypical reversed pressure-induced phase transformation in Ge nanowires.

Phase transformations of Ge under compression/decompression cycle at room temperature were studied in a diamond anvil cell (DAC) using in situ synchrotron x-ray diffraction, Raman spectroscopy and near infrared absorption techniques. Upon compression similar behavior is observed in nanowires and in bulk although a higher stability is observed in nanowires. The cubic-diamond phase (Ge-3C), the most energetically favorable phase, transforms into the ß-tin metallic phase at high pressure and the reverse Ge-ß-tin to Ge-3C transformation is generally inhibited by kinetics when pressure is released. While the transformation in Ge bulk leads mostly to Ge-ST12 phase, the loading/unloading cycle of Ge nanowires in DAC leads back to Ge-3C, exhibiting unprecedented size effects. A comprehensive characterization of the final states is described.

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.

Commissioning of a multi-beamline femtoslicing facility at SOLEIL.

The investigation of ultrafast dynamics, taking place on the few to sub-picosecond time scale, is today a very active research area pursued in a variety of scientific domains. With the recent advent of X-ray free-electron lasers (XFELs), providing very intense X-ray pulses of duration as short as a few femtoseconds, this research field has gained further momentum. As a consequence, the demand for access strongly exceeds the capacity of the very few XFEL facilities existing worldwide. This situation motivates the development of alternative sub-picosecond pulsed X-ray sources among which femtoslicing facilities at synchrotron radiation storage rings are standing out due to their tunability over an extended photon energy range and their high stability. Following the success of the femtoslicing installations at ALS, BESSY-II, SLS and UVSOR, SOLEIL decided to implement a femtoslicing facility. Several challenges were faced, including operation at the highest electron beam energy ever, and achievement of slice separation exclusively with the natural dispersion function of the storage ring. SOLEIL's setup also enables, for the first time, delivering sub-picosecond pulses simultaneously to several beamlines. This last feature enlarges the experimental capabilities of the facility, which covers the soft and hard X-ray photon energy range. In this paper, the commissioning of this original femtoslicing facility is reported. Furthermore, it is shown that the slicing-induced THz signal can be used to derive a quantitative estimate for the degree of energy exchange between the femtosecond infrared laser pulse and the circulating electron bunch.

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.

Design of low density SNP chips for genotype imputation in layer chicken.

BACKGROUND: The main goal of selection is to achieve genetic gain for a population by choosing the best breeders among a set of selection candidates. Since 2013, the use of a high density genotyping chip (600K Affymetrix® Axiom® HD genotyping array) for chicken has enabled the implementation of genomic selection in layer and broiler breeding, but the genotyping costs remain high for a routine use on a large number of selection candidates. It has thus been deemed interesting to develop a low density genotyping chip that would induce lower costs. In this perspective, various simulation studies have been conducted to find the best way to select a set of SNPs for low density genotyping of two laying hen lines. RESULTS: To design low density SNP chips, two methodologies, based on equidistance (EQ) or on linkage disequilibrium (LD) were compared. Imputation accuracy was assessed as the mean correlation between true and imputed genotypes. The results showed correlations more sensitive to false imputation of SNPs having low Minor Allele Frequency (MAF) when the EQ methodology was used. An increase in imputation accuracy was obtained when SNP density was increased, either through an increase in the number of selected windows on a chromosome or through the rise of the LD threshold. Moreover, the results varied depending on the type of chromosome (macro or micro-chromosome). The LD methodology enabled to optimize the number of SNPs, by reducing the SNP density on macro-chromosomes and by increasing it on micro-chromosomes. Imputation accuracy also increased when the size of the reference population was increased. Conversely, imputation accuracy decreased when the degree of kinship between reference and candidate populations was reduced. Finally, adding selection candidates' dams in the reference population, in addition to their sire, enabled to get better imputation results. CONCLUSIONS: Whichever the SNP chip, the methodology, and the scenario studied, highly accurate imputations were obtained, with mean correlations higher than 0.83. The key point to achieve good imputation results is to take into account chicken lines' LD when designing a low density SNP chip, and to include the candidates' direct parents in the reference population.

Nuclear Spin Symmetry Conservation in 1H216O Investigated by Direct Absorption FTIR Spectroscopy of Water Vapor Cooled Down in Supersonic Expansion.

We report the results of an experimental study related to the relaxation of the nuclear spin isomers of the water molecule in a supersonic expansion. Rovibrational lines of both ortho and para spin isomers were recorded in the spectral range of H2O stretching vibrations at around 3700 cm-1 using FTIR direct absorption. Water vapor seeded in argon, helium, or oxygen or in a mixture of oxygen and argon was expanded into vacuum through a slit nozzle. The water vapor partial pressure in the mixture varied over a wide range from 1.5 to 102.7 hPa, corresponding to a water molar fraction varying between 0.2 and 6.5%. Depending on expansion conditions, the effect of water vapor clustering was clearly seen in some of our measured spectra. The Boltzmann plot of the line intensities allowed the H2O rotational temperatures in the isentropic core and in the lateral shear layer probed zones of the planar expansion to be determined. The study of the OPR, i.e., the ratio of the ortho to para absorption line intensities as a function of Trot, did not reveal any signs of the OPR being relaxed to the sample temperature. In contrast, the OPR was always conserved according to the stagnation reservoir equilibrium temperature. The conservation of the OPR was found irrespective of whether water molecule clustering was pronounced or not. Also, no effect of the paramagnetic oxygen admixture enhancing OPR relaxation was observed.

Water in Carbon Nanotubes: The Peculiar Hydrogen Bond Network Revealed by Infrared Spectroscopy.

A groundbreaking discovery in nanofluidics was the observation of the tremendously enhanced water permeability of carbon nanotubes, those iconic objects of nanosciences. The origin of this phenomenon is still a subject of controversy. One of the proposed explanations involves dramatic modifications of the H-bond network of nanoconfined water with respect to that of bulk water. Infrared spectroscopy is an ideal technique to follow modifications of this network through the inter- and intramolecular bonds of water molecules. Here we report the first infrared study of water uptake at controlled vapor pressure in single walled carbon nanotubes with diameters ranging from 0.7 to 2.1 nm. It reveals a predominant contribution of loose H bonds even for fully hydrated states, irrespective of the nanotube size. Our results show that, while the dominating loosely bond signature is attributed to a one-dimensional chain structure for small diameter nanotubes, this feature also results from a water layer with "free" OH (dangling) bonds facing the nanotube wall for larger diameter nanotubes. These experimental findings provide a solid reference for further modeling of water behavior in hydrophobic nanochannels.

GWAS analyses reveal QTL in egg layers that differ in response to diet differences.

BACKGROUND: The genetic architecture of egg production and egg quality traits, i.e. the quantitative trait loci (QTL) that influence these traits, is still poorly known. To date, 33 studies have focused on the detection of QTL for laying traits in chickens, but less than 10 genes have been identified. The availability of a high-density SNP (single nucleotide polymorphism) chicken array developed by Affymetrix, i.e. the 600K Affymetrix(®) Axiom(®) HD genotyping array offers the possibility to narrow down the localization of previously detected QTL and to detect new QTL. This high-density array is also anticipated to take research beyond the classical hypothesis of additivity of QTL effects or of QTL and environmental effects. The aim of our study was to search for QTL that influence laying traits using the 600K SNP chip and to investigate whether the effects of these QTL differed between diets and age at egg collection. RESULTS: One hundred and thirty-one QTL were detected for 16 laying traits and were spread across all marked chromosomes, except chromosomes 16 and 25. The percentage of variance explained by a QTL varied from 2 to 10 % for the various traits, depending on diet and age at egg collection. Chromosomes 3, 9, 10 and Z were overrepresented, with more than eight QTL on each one. Among the 131 QTL, 60 had a significantly different effect, depending on diet or age at egg collection. For egg production traits, when the QTL × environment interaction was significant, numerous inversions of sign of the SNP effects were observed, whereas for egg quality traits, the QTL × environment interaction was mostly due to a difference of magnitude of the SNP effects. CONCLUSIONS: Our results show that numerous QTL influence egg production and egg quality traits and that the genomic regions, which are involved in shaping the ability of layer chickens to adapt to their environment for egg production, vary depending on the environmental conditions. The next question will be to address what the impact of these genotype × environment interactions is on selection.

Standard free energy of the equilibrium between the trans-monomer and the cyclic-dimer of acetic acid in the gas phase from infrared spectroscopy.

Survey jet-cooled spectra of acetic acid have been recorded in the infrared region (200-4000 cm(-1)) over a wide range of expansion conditions. From the variations of the relative intensities of the signals, vibrational transitions have been assigned unambiguously to the trans-monomer and cyclic-dimer. The IR-active fundamental frequencies have been determined at the instrumental accuracy of 0.5 cm(-1). This analysis of the jet-cooled spectra supported by electronic structure calculations permitted us to characterize the trans-monomer/cyclic-dimer equilibrium. From static cell spectra at 298 K, variations of the molar fractions ratio as a function of the total pressure were used to estimate the equilibrium constant and the Gibbs free energy of dimerization at 298 K. The very good agreement with the literature data shows that the present method is able to produce, from a single study, a free energy value as reliable as the one obtained from a large collection of data. In addition, the semi-empirical free energy value was used to estimate the accuracy of electronic structure calculations and in turn the accuracy of the derived useful information such as the dissociation energy of the complex (i.e. the strength of the hydrogen bonds) or the relative energies within the conformational landscape.

QTL detection for coccidiosis (Eimeria tenella) resistance in a Fayoumi × Leghorn F2 cross, using a medium-density SNP panel.

BACKGROUND: Coccidiosis is a major parasitic disease that causes huge economic losses to the poultry industry. Its pathogenicity leads to depression of body weight gain, lesions and, in the most serious cases, death in affected animals. Genetic variability for resistance to coccidiosis in the chicken has been demonstrated and if this natural resistance could be exploited, it would reduce the costs of the disease. Previously, a design to characterize the genetic regulation of Eimeria tenella resistance was set up in a Fayoumi × Leghorn F2 cross. The 860 F2 animals of this design were phenotyped for weight gain, plasma coloration, hematocrit level, intestinal lesion score and body temperature. In the work reported here, the 860 animals were genotyped for a panel of 1393 (157 microsatellites and 1236 single nucleotide polymorphism (SNP) markers that cover the sequenced genome (i.e. the 28 first autosomes and the Z chromosome). In addition, with the aim of finding an index capable of explaining a large amount of the variance associated with resistance to coccidiosis, a composite factor was derived by combining the variables of all these traits in a single variable. QTL detection was performed by linkage analysis using GridQTL and QTLMap. Single and multi-QTL models were applied. RESULTS: Thirty-one QTL were identified i.e. 27 with the single-QTL model and four with the multi-QTL model and the average confidence interval was 5.9 cM. Only a few QTL were common with the previous study that used the same design but focused on the 260 more extreme animals that were genotyped with the 157 microsatellites only. Major differences were also found between results obtained with QTLMap and GridQTL. CONCLUSIONS: The medium-density SNP panel made it possible to genotype new regions of the chicken genome (including micro-chromosomes) that were involved in the genetic control of the traits investigated. This study also highlights the strong variations in QTL detection between different models and marker densities.

Gibbs free energy of liquid water derived from infrared measurements.

Infrared spectra of pure liquid water were recorded from 20 cm(-1) to 4000 cm(-1) at temperatures ranging from 263 K to 363 K. The evolution of connectivity, libration, bending and OH stretching bands as a function of temperature follows the evolution of the inter-molecular dynamics, and so gives insight into the internal energy averaged over the measurement time and space. A partition function, which takes into account the inter-molecular and intra-molecular modes of vibration of water, all variable with the molecular networking, was developed to convert this vibrational absorption behavior of water into its macroscopic Gibbs free energy, assuming the vibrational energy to feature most of the water energy. Calculated Gibbs free energies along the thermal range are in close agreement with the literature values up to 318 K. Above this temperature, contributions specific to the non H-bonded molecules must be involved to closely fit the thermodynamics of water. We discussed this temperature threshold in relation to the well-known isosbestic point. Generally speaking, our approach is valuable to convert the IR molecular data into mean field properties, a quantitative basis to predict how water behaves in natural or industrial settings.

Confined H2O molecules as local probes of pressure-induced amorphisation in faujasite.

Confined H2O molecules act as local probes for depressurization phenomena during the pressure induced amorphisation of faujasite NaX at which the OH stretching frequency first decreases and then increases almost to its room pressure value upon further compression. Pair distribution function (PDF) analysis provides evidence that amorphisation corresponds to a collapse of the structure around hydrated sodium cations with strong distortion of the secondary building units (double six-membered rings, sodalite cages). Both the use of guest molecules as local probes in far- and mid-infrared spectroscopy, where we correlate intermolecular water H bonding vibrations and internal mode behaviour under confinement, and PDF analysis could be of great use to study the mechanical behaviour of other hydrated materials.