A combined inelastic neutron scattering and simulation study of the 3He@C60 endofullerene.

The 3He@C60 endofullerene consists of a single 3He atom entrapped inside a C60 fullerene cage. The confining potential, arising from the non-covalent interaction between the enclosed He atom and the C atoms of the cage, is investigated by inelastic neutron scattering. These measurements allow us to obtain information in both energy (ω) and momentum (Q) transfers in the form of the dynamical structure factor S (Q, ω). Simulations of the S (Q, ω) maps are performed for a spherical anharmonic oscillator model. Good agreement between the experimental and simulated data sets is achieved.

Experimental and Modeling Studies of Local and Nanoscale para-Cresol Behavior: A Comparison of Classical Force Fields.

The dynamics of bulk liquid para-cresol from 340-390 K was probed using a tandem quasielastic neutron scattering (QENS) and molecular dynamics (MD) approach, due to its relevance as a simple model component of lignin pyrolysis oil. QENS experiments observed both translational jump diffusion and isotropic rotation, with diffusion coefficients ranging from 10.1 to 28.6 × 10-10 m2s-1 and rotational rates from 5.7 to 9.2 × 1010 s-1. The associated activation energies were 22.7 ± 0.6 and 10.1 ± 1.2 kJmol-1 for the two different dynamics. MD simulations applying two different force field models (OPLS3 and OPLS2005) gave values close to the experimental diffusion coefficients and rotational rates obtained upon calculating the incoherent dynamic structure factor from the simulations over the same time scale probed by the QENS spectrometer. The simulations gave resulting jump diffusion coefficients that were slower by factors of 2.0 and 3.8 and rates of rotation that were slower by factors of 1.2 and 1.6. Comparing the two force field sets, the OPLS3 model showed slower rates of dynamics likely due to a higher molecular polarity, leading to greater quantities and strengths of hydrogen bonding.

Differentiating the role of organic additives to assemble open framework aluminosilicates using INS spectroscopy.

Presently, there is little clarity concerning how organic additives control structure formation in the synthesis of zeolite catalysts. Such ambiguity is a major obstacle towards synthesis design of new bespoke zeolites with intended applications. Herein, we have applied inelastic neutron scattering (INS) spectroscopy to experimentally probe the nature of organic-framework interactions, which are crucial in understanding structure direction. With this technique we have studied the dynamics of 18-crown-6 ether, which can be used as an additive to direct the formation of four zeolites: Na-X, EMC-2, RHO and ZK-5. We observed significant softening of the 18-crown-6 ether molecule's dynamics upon occlusion within a zeolite host, with a strong influence on both the circular and radial vibrational modes. Furthermore, there is a strong correlation between the size/geometry of the zeolite framework cages and perturbations in the dynamics of the 18C6 oxyethylene chain. We propose that the approach used herein can be used to study other zeolites, and hence gain a more comprehensive view of organic-framework interactions.

Affecting an Ultra-High Work Function of Silver.

An ultra-high increase in the WF of silver, from 4.26 to 7.42 eV, that is, an increase of up to circa 3.1 eV is reported. This is the highest WF increase on record for metals and is supported by recent computational studies which predict the potential ability to affect an increase of the WF of metals by more than 4 eV. We achieved the ultra-high increase by a new approach: Rather than using the common method of 2D adsorption of polar molecules layers on the metal surface, WF modifying components, l-cysteine and Zn(OH)2 , were incorporated within the metal, resulting in a 3D architecture. Detailed material characterization by a large array of analytical methods was carried out, the combination of which points to a WF enhancement mechanism which is based on directly affecting the charge transfer ability of the metal separately by cysteine and hydrolyzed zinc(II), and synergistically by the combination of the two through the known Zn-cysteine finger redox trap effect.

Thermal and Structural Aspects of the Hydride-Conducting Oxyhydride La2LiHO3 Obtained via a Halide Flux Method.

Oxyhydrides, in which oxide and hydride anions share the same anionic lattice, are relatively rare compounds. La2LiHO3 belongs to this family. We report the synthesis of La2LiHO3 by means of an alkali halide flux method, which allows the production of larger quantities of material relative to the usually adopted synthesis routes. Powder X-ray and neutron diffraction studies show that La2LiHO3 adopts an n = 1 Ruddlesden-Popper (RP)-type structure with an orthorhombic distortion (Immm) due to hydride and oxide anion ordering. No sign of polymorphism is observed. La2LiHO3 is seen to decompose in an oxygen atmosphere at ∼450 °C into La2LiO3.5. We show that the high mobility of hydride anions close to the decomposition temperature is likely the main factor in inducing the oxidation. The crystal structure of La2LiO3.5 is also determined and takes an n = 1 RP-type structure with an orthorhombic distortion (Fmmm). This newly reported large-scale synthesis approach, combined with the proven high thermal stability, is a key factor for potential practical applications of this oxyhydride in real devices.

Thermal transport across nanoparticle-fluid interfaces: the interplay of interfacial curvature and nanoparticle-fluid interactions.

We investigate the general dependence of the thermal transport across nanoparticle-fluid interfaces using molecular dynamics computations. We show that the thermal conductance depends strongly both on the wetting characteristics of the nanoparticle-fluid interface and on the nanoparticle size. Strong nanoparticle-fluid interactions, leading to full wetting states in the host fluid, result in high thermal conductances and efficient interfacial transport of heat. Weak interactions result in partial drying or full drying states, and low thermal conductances. The variation of the thermal conductance with particle size is found to depend on the fluid-nanoparticle interactions. Strong interactions coupled with large interfacial curvatures lead to optimum interfacial heat transport. This complex dependence can be modelled using an equation that includes the interfacial curvature as a parameter. In this way, we rationalise the existing experimental and computer simulation results and show that the thermal transport across nanoscale interfaces is determined by the correlations of both interfacial curvature and nanoparticle-fluid interactions.

Heads or tails: how do chemically substituted fullerenes melt?

We address the question as to whether the melting of chemically substituted fullerenes is driven by the dynamics of the fullerene moiety (the head) or the substituted sub-unit (the tail). To this end, we have performed quasielastic neutron-scattering experiments and classical molecular-dynamics simulations as a function of temperature on the prototypical fullerene derivative phenyl-C61-butyric acid methyl ester. To enable a direct and quantitative comparison between experimental and simulation data, dynamic structure factors for the latter have been calculated from atomic trajectories and further convolved with the known instrument response. A detailed analysis of the energy- and momentum-transfer dependence of this observable in the quasielastic regime shows that melting is entirely driven by temperature-activated tail motions. We also provide quantitative estimates of the activation energy for this process as the material first enters a plastic-crystalline phase, followed by the emergence of a genuine liquid at higher temperatures.

The rich phase behavior of the thermopolarization of water: from a reversal in the polarization, to enhancement near criticality conditions.

We investigate using non-equilibrium molecular dynamics simulations the polarization of water induced by thermal gradients using the accurate TIP4P/2005 water model. The full dependence of the polarization covering a wide range of thermodynamic states, from near supercritical to ambient conditions, is reported. Our results show a strong dependence of the thermo-polarization field with the thermodynamic state. The field features a strong enhancement near the critical point, which can be rationalized in terms of the large increase and ultimately the divergence of the thermal expansion of the fluid at the critical temperature. We also show that the TIP4P/2005 model features a reversal in the sign of the thermal polarization at densities ∼1 g cm(-3). The latter result is consistent with the recent observation of this reversal phenomenon in SPC/E water and points the existence of this general physical phenomenon in water.

Thermal conductivity of highly asymmetric binary mixtures: how important are heat/mass coupling effects?

The coupling of mass and heat fluxes is responsible for the Soret effect in fluid mixtures containing particles of dissimilar mass and/or size. We investigate using equilibrium and non-equilibrium molecular dynamics simulations the relevance of these coupling effects in determining the thermal transport in fluids consisting of binary mixtures where the individual components feature significant mass, 1 : 8, or size, 1 : 3, asymmetries. We quantify the thermal transport by using both boundary driven molecular dynamics simulations (NEMD) and the equilibrium Green-Kubo (GK) approach and investigate the impact of different heat flux definitions, relevant in kinetic theory and experiments, in the quantification of the thermal conductivity. We find that the thermal conductivities obtained from the different definitions agree within numerical accuracy, suggesting that the Soret coefficient does not lead to significant changes in the thermal conduction, even for the large asymmetries considered here, which lead to significant Soret coefficients (∼10(-2) K(-1)). The asymmetry in size and mass introduces large differences in the specific enthalpy of the individual components that must be carefully considered to compute accurate thermal conductivities using the GK approach. Neglecting the enthalpic contributions, results in large overestimations of the thermal conductivity, typically between 20% and 50%. Further, we quantify the time dependent behavior of the internal energy and mass flux correlation functions and propose a microscopic mechanism for the heat transport in these asymmetric mixtures.

The Advantages of Flexibility: The Role of Entropy in Crystal Structures Containing C-H···F Interactions.

Molecular crystal structures are often interpreted in terms of strong, structure directing, intermolecular interactions, especially those with distinct geometric signatures such as H-bonds or π-stacking interactions. Other interactions can be overlooked, perhaps because they are weak or lack a characteristic geometry. We show that although the cumulative effect of weak interactions is significant, their deformability also leads to occupation of low energy vibrational energy levels, which provides an additional stabilizing entropic contribution. The entropies of five fluorobenzene derivatives have been calculated by periodic DFT calculations to assess the entropic influence of C-H···F interactions in stabilizing their crystal structures. Calculations reproduce inelastic neutron scattering data and experimental entropies from heat capacity measurements. C-H···F contacts are shown to have force constants which are around half of those of more familiar interactions such as hydrogen bonds, halogen bonds, and C-H···π interactions. This feature, in combination with the relatively high mass of F, means that the lowest energy vibrations in crystalline fluorobenzenes are dominated by C-H···F contributions. C-H···F contacts occur much more frequently than would be expected from their enthalpic contributions alone, but at 150 K, the stabilizing contribution of entropy provides, at -10 to -15 kJ mol-1, a similar level of stabilization to the N-H···N hydrogen bond in ammonia and O-H···O hydrogen bond in water.

Cation Dynamics as Structure Explorer in Hybrid Perovskites-The Case of MAPbI3.

Hybrid organic-inorganic perovskites exhibit remarkable potential as cost-effective and high-efficiency materials for photovoltaic applications. Their exceptional chemical tunability opens further routes for optimizing their optical and electronic properties through structural engineering. Nevertheless, the extraordinary softness of the lattice, stemming from its interconnected organic-inorganic composition, unveils formidable challenges in structural characterization. Here, by focusing on the quintessential methylammonium lead triiodide, MAPbI3, we combine first-principles modeling with high-resolution neutron scattering data to identify the key stationary points on its shallow potential energy landscape. This combined experimental and computational approach enables us to benchmark the performance of a collection of semilocal exchange-correlation functionals and to track the local distortions of the perovskite framework, hallmarked by the inelastic neutron scattering response of the organic cation. By conducting a thorough examination of structural distortions, we introduce the IKUR-PVP-1 structural data set. This data set contains nine mechanically stable structural models, each manifesting a distinct vibrational response. IKUR-PVP-1 constitutes a valuable resource for assessing thermal behavior in the low-temperature perovskite phase. In addition, it paves the way for the development of accurate force fields, enabling a comprehensive understanding of the interplay between the structure and dynamics in MAPbI3 and related hybrid perovskites.

Cation Dynamics and Structural Stabilization in Formamidinium Lead Iodide Perovskites.

The vibrational dynamics of pure and methylammonium-doped formamidinium lead iodide perovskites (FAPbI3) has been investigated by high-resolution neutron spectroscopy. For the first time, we provide an exhaustive and accurate analysis of the cation vibrations and underlying local structure around the organic moiety in these materials using first-principles electronic-structure calculations validated by the neutron data. Inelastic neutron scattering experiments on FAPbI3 provide direct evidence of the formation of a low-temperature orientational glass, unveiling the physicochemical origin of phase metastability in the tetragonal structure. Further analysis of these data provides a suitable starting point to explore and understand the stabilization of the perovskite framework via doping with small amounts of organic cations. In particular, we find that the hydrogen-bonding interactions around the formamidinium cations are strengthened as a result of cage deformation. This synergistic effect across perovskite cages is accompanied by a concomitant weakening of the methylammonium interactions with the surrounding framework.

Using acoustic telemetry to quantify potential contaminant exposure of Vermilion Rockfish (Sebastes miniatus), Hornyhead Turbot (Pleuronichthys verticalis), and White Croaker (Genyonemus lineatus) at wastewater outfalls in southern California.

Contaminant Exposure Models (CEMs) were developed to predict population-level tissue contaminant concentrations in fishes by pairing sediment-bound contaminant concentrations (DDTs, PCBs) and fine-scale acoustic telemetry data from a habitat-associated species (Vermilion Rockfish, Sebastes miniatus), nomadic flatfish species (Hornyhead Turbot, Pleuronichthys verticalis), and nomadic benthic/midwater schooling species (White Croaker, Genyonemus lineatus) tagged near wastewater outfalls in southern California. Model results were compared to contaminant concentrations in tissue samples. The CEMs developed require further refinement before implementation into management efforts but may act as steppingstones to help shift primary monitoring methods away from the regular field collection of fish for tissue contaminant analyses and towards behavioral modeling and habitat mapping. We also developed Kernel Density Estimates that can be used by managers immediately to identify regions that contribute most to contaminant exposure in species of concern. Prioritizing remediation efforts in these areas are likely to be most effective at improving fish health.

Vibrational Motions Make Significant Contributions to Sequential Methyl C-H Activations in an Organometallic Complex.

[(Pentamethylcyclopentadienyl)Rh(III)(bipyridine)(chloride)]+ (Cp*Rh-Cl) undergoes sequential deuteriation of its 15 Cp* CH groups in polar deuterated solvents. Vibrational spectra of H14-Cp*Rh-Cl and D14-Cp*Rh-Cl were captured via inelastic neutron spectroscopy (INS) and assigned using density functional theory (DFT) phonon calculations. These calculations were precisely weighted to the spectrometer's neutronic response. The Cp* ring behaves as a moving carousel, bringing each CH3 close to the Rh-OH/D center where proton abstraction occurs. Vibrations relevant for carousel movement and proximal positioning for H transfer were identified. DFT modeling uncovered changes in vibrations along the reaction path, involving a Rh(I)-fulvene intermediate. Vibronic energy contributions are large across the entire transition. Remarkably, they amount to over a 400-fold increase in the proton transfer rate. The inclusion of vibrational degrees of freedom could be applied more widely to catalysts and molecular machines to harness the energetics of these vibrations and increase their effective rates of operation.

Ecological effects of wastewater treatment modifications on infauna communities off the coast of Orange County, California.

The Orange County Sanitation District (OCSD) is a public agency that provides treatment of wastewater for residents in Orange County, California. The final effluent characteristics at OCSD have been altered in the last 18 years due to the ~20-fold increase of sodium hypochlorite usage for disinfecting waste streams from 2002 to 2010, implementation of the Ground Water Replenishment System (GWRS) in 2008, and conversion to full secondary treatment, together with a major reduction of sodium hypochlorite usage in 2011. This study analyzed infauna data gathered from 1994 to 2016 at the zone of initial dilution (ZID) and reference stations located on the San Pedro Shelf to assess the effects of these treatment process changes on biota in the receiving water. Impacts to the infauna community within the ZID were observed during the period of high chlorine usage, including the increased proportion of the pollution tolerant polychaete Capitella capitata complex from 6.2% in 2003 to nearly 60% in 2010, the lowest Infaunal Trophic Index score in 2009, and the highest Benthic Response Index score in 2006. The degradation of the infauna community in the ZID was correlated with chlorination and was coincidental with the initiation of the GWRS. The infauna community at the ZID recovered rapidly after the implementation of full secondary treatment as indicated by the significant reduction of the relative abundance of C. capitata complex from 59.8% in 2010 to less than 0.1% after 2012, and by the markedly improved community health index scores. This study demonstrated the composition and biointegrity of the infauna community at the ZID varied in response to changes in the wastewater treatment process. Caution should be exercised at wastewater treatment plants when relatively higher dosages of sodium hypochlorite are used over a multi-year period, as this may negatively impact aquatic biota in the receiving water.

Deep-Glassy Ice VI Revealed with a Combination of Neutron Spectroscopy and Diffraction.

The recent discovery of a low-temperature endotherm upon heating hydrochloric-acid-doped ice VI has sparked a vivid controversy. The two competing explanations aiming to explain its origin range from a new distinct crystalline phase of ice to deep-glassy states of the well-known ice VI. Problems with the slow kinetics of deuterated phases have been raised, which we circumvent here entirely by simultaneously measuring the inelastic neutron spectra and neutron diffraction data of H2O samples. These measurements support the deep-glassy ice VI scenario and rule out alternative explanations. Additionally, we show that the crystallographic model of D2O ice XV, the ordered counterpart of ice VI, also applies to the corresponding H2O phase. The discovery of deep-glassy ice VI now provides a fascinating new example of ultrastable glasses that are encountered across a wide range of other materials.

Site-specific effects of 17beta-estradiol in hornyhead turbot (Pleuronichthys verticalis) collected from a wastewater outfall and reference location.

Studies throughout the southern California bight have indicated persistent estrogenic activity in male hornyhead turbot (Pleuronichthys verticalis). Plasma 17beta-estradiol (E2) concentrations correlated with gonadal DNA damage in fish collected near a wastewater treatment plant outfall, but not from fish collected at the reference location. When the same species was collected from the same reference location and treated with E2, no relationship between uptake and gonadal DNA damage was observed. To evaluate the site-specific effects of E2 in fish from a wastewater outfall and fish from a reference location, male hornyhead turbot from each location were exposed to 15 microg/L aqueous E2 in a time-course experiment, with fish sampled every 12 h for 48 h. Concentrations of E2 were measured in the aqueous exposure and in plasma from the fish. Vitellogenin (vtg) was also measured in the plasma, and 8-oxo-7,8-dihydro-2'-deoxyguanosine levels in male gonads were measured as an indicator of DNA damage. Untreated fish from the outfall had significantly lower E2 in the plasma relative to the untreated reference fish, and this trend was consistent at each time point in the E2-treated fish. Vtg was significantly induced after 36 h of exposure in fish from both sites and no significant differences were observed between the sites. A significant increase of oxidative DNA damage was observed in E2-treated fish from the outfall population and the damage was significantly correlated with plasma E2 concentrations only in fish from the outfall after 48 h. These results indicated that there were significant differences in E2 disposition and gonadal genotoxicity between the hornyhead turbot populations following exposure to E2, suggesting that fish at wastewater outfalls may be more sensitive to DNA damage, which may be temporally related to concentrations of E2 in plasma.

Chasing the "Killer" Phonon Mode for the Rational Design of Low-Disorder, High-Mobility Molecular Semiconductors.

Molecular vibrations play a critical role in the charge transport properties of weakly van der Waals bonded organic semiconductors. To understand which specific phonon modes contribute most strongly to the electron-phonon coupling and ensuing thermal energetic disorder in some of the most widely studied high-mobility molecular semiconductors, state-of-the-art quantum mechanical simulations of the vibrational modes and the ensuing electron-phonon coupling constants are combined with experimental measurements of the low-frequency vibrations using inelastic neutron scattering and terahertz time-domain spectroscopy. In this way, the long-axis sliding motion is identified as a "killer" phonon mode, which in some molecules contributes more than 80% to the total thermal disorder. Based on this insight, a way to rationalize mobility trends between different materials and derive important molecular design guidelines for new high-mobility molecular semiconductors is suggested.

Direct microwave transesterification of fingertip prick blood samples for fatty acid determinations.

Omega-3 polyunsaturated fatty acid (PUFA) dietary intakes and tissue levels are positively associated with various health benefits. The development of cost efficient, high throughput methodologies would enable research in large clinical and population studies, and clinical fatty acid profiling. Microwave heating for the transesterification of blood fatty acids was examined. Samples were collected by venous puncture and fingertip prick onto chromatography paper. Aliquots of serum, plasma, erythrocytes and whole blood were prepared from venous blood. Boron trifluoride in methanol was used for transesterification but sample preparation and heating varied. Fatty acid determinations and markers of omega-3 fatty acid status including the sum of eicosapentaenoic acid and docosahexaenoic acid, the ratio of total n-3 PUFA to n-6 PUFA, and the percentage of n-3 highly unsaturated fatty acids (HUFA, >or=20 carbons and >or=3 carbon-carbon double bonds) in total HUFA were compared. Quantitative determinations indicate that microwave transesterification results in significantly lower estimates of monounsaturates and polyunsaturates, possibly through incomplete transesterification of triacylglycerols. However, qualitative estimates of omega-3 fatty acid status were relatively similar. Fingertip prick blood collection combined with direct transesterification by microwave may be a very rapid method to estimate omega-3 fatty acid status for selected applications.

Uptake of estradiol from sediment by hornyhead turbot (Pleuronichthys verticalis) and effects on oxidative DNA damage in male gonads.

Male and female hornyhead turbot (Pleuronichthys verticalis) were exposed to four concentrations (0, 0.75, 14.7 and 46.5 ng/g dry weight) of E2-amended sediment for 7 days. Sediment-derived E2 was bioavailable to the flatfish, though the route of uptake was unclear. A concentration of 46.5 ng/g E2 in sediment led to a significant increase in vitellogenin concentrations in the plasma in both sexes after 7 days of exposure. Though plasma E2 concentrations increased significantly in males at sediment E2 concentrations of 0.75 ng/g dry weight and above, a dose-dependent increase was not observed. There was also no correlation between sediment E2 concentrations, plasma E2 concentrations, and oxidative DNA damage in male gonads. The results suggest that the DNA damage previously seen in the gonads of feral hornyhead turbot at a sewage outfall is likely not caused by acute exposure to exogenous E2 from sediments.