<Emphasis Type="Italic">In situ</Emphasis> X-ray and neutron diffraction study of lipid membrane swelling

Liposome suspensions comprising the synthetic cationic lipid DOTAP, the zwitterionic DPPC and the anti-cancer agent Paclitaxel were deposited on solid substrates and investigated by X-ray and neutron reflectivity measurements at ESRF and ILL. Well ordered multilamellar drug/lipid membranes were obtained, such as indicated by the several orders of Bragg reflections in the diffraction pattern. With an excess of Paclitaxel, additional Bragg peaks from the drug crystalline phase could be observed. Changes of the molecular organization in the drug-lipid system were investigated as a function of relative humidity using a custom-built controlled humidity chamber. For DOTAP multilayers the effects of bilayer swelling were much more pronounced than for DPPC under similar conditions, while the crystalline peaks of the drug were not affected. The pronounced swelling of DOTAP multilayers might be related to the electrostatic repulsion between the charged lipid headgroups.     

Structure-property relations in crystalline L-leucine obtained from calorimetry, X-rays, neutron and Raman scattering

We have studied the amino acid L-leucine (LEU) using inelastic neutron scattering, X-rays and neutron diffraction, calorimetry and Raman scattering as a function of temperature, focusing on the relationship between the local dynamics of the NH(3), CH(3), CH(2) and CO(2) moieties and the molecular structure of LEU. Calorimetric and diffraction data evidenced two novel phase transitions at about 150 K (T(1)) and 275 K (T(2)). The dynamical susceptibility function, obtained from the inelastic neutron scattering results, shows a re-distribution of the intensity of the vibrational bands that can be directly correlated with the phase transitions observed at T(1) and T(2), as well as with the already reported phase transition at T(3) = 353 K. Through the analysis of the Raman modes, the new structural arrangement observed below T(1) was related to conformational modifications of the CH and CH(3) groups, while the behavior of the N-H stretching vibration, ν(NH(3)), gave insight into the intermolecular N-H…O interactions. The observation of changes in the translational symmetry in the crystalline lattice, as well as anharmonic dynamics, allows for localized motions in LEU.     

Structural isotopic effects in the smallest chiral amino acid: observation of a structural phase transition in fully deuterated alanine

A first study of possible changes instigated by deuteration in amino acids was carried out using neutron diffraction, inelastic neutron scattering, and Raman scattering in l-alanine, C2H4(NH2)COOH. Careful analysis of the structural parameters shows that deuteration of l-alanine engenders significant geometric changes as a function of temperature, which can be directly related to the observation of new lattice vibration modes in the Raman spectra. The combination of the experimental data suggests that C2D4(ND2)COOD undergoes a structural phase transition (or a structural rearrangement) at about 170 K. Considering that this particular amino acid is a hydrogen-bonded system with short hydrogen bonds (O...H approximately 1.8 A), we evoke the Ubbelohde effect to conclude that substitution of hydrogen for deuterium gives rise to changes in the hydrogen-bonding interactions. The structural differences suggest distinct relative stabilities for the hydrogenous and deuterated l-alanine.     

High‐pressure Raman spectra of deuterated L‐alanine crystal

Raman spectra of deuterated L ‐alanine have been obtained at high‐pressure conditions. A phase transition at ∼1.5 GPa associated with the splitting of some internal modes and increase of the wavenumber of the external modes was observed. Similarly to the hydrogenated L ‐alanine crystal, this first transition was related to a symmetry change. Moreover, further modifications of the Raman spectra were observed at 4.4 GPa, which may be associated to conformational changes of the molecule. To give further support to such a hypothesis, neutron powder diffraction measurements were performed. Information about the cell parameter at atmospheric pressure gave valuable information about the N D distances, shedding light on the behavior of the torsional vibration of ND₃⁺. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational Analysis of the Elpasolites Cs2NaAlF6 and Cs2NaGaF6 Doped with Cr3+ Ions by Fluorescence Spectroscopy

Interest in 3d transition metal impurities in ionic crystals has increased due to their important role in the laser activity of these materials. Moreover, recent advances in tunable solid-state lasers and high-power semiconductor laser diode arrays have generated a strong interest in investigating new compounds that emit in the visible and near-infrared spectral regions. In particular, many optical studies have been devoted to Cr³⁺-doped fluoride crystals as a consequence of the high quality of some Cr³⁺-based laser materials. In the present investigation, the low-temperature emission spectra of Cr³⁺ ions in the hexagonal elpasolites Cs₂NaAlF₆ and Cs₂NaGaF₆ have been measured. Each compound has two crystallographically inequivalent octahedral sites for the Al³⁺ and Ga³⁺ ions that can be occupied by Cr³⁺ ions. For both materials, the luminescence spectrum presents two zero-phonon lines accompanied by a well-defined vibrational structure. The different peaks of the emission broad band are described in terms of phonons of the lattice and normal modes of the octahedral complex [CrF₆]^3–. A detailed analysis of the vibrational structure observed leads to the conclusion that the ² E and ⁴ T ₂ excited states of the [CrF₆]^3– ion are displaced along the e _g and a _1g and probably the t _2g coordinates.     

Water dynamics in hardened ordinary Portland cement paste or concrete: from quasielastic neutron scattering

Portland cement reacts with water to form an amorphous paste through a chemical reaction called hydration. In concrete the formation of pastes causes the mix to harden and gain strength to form a rock-like mass. Within this process lies the key to a remarkable peculiarity of concrete: it is plastic and soft when newly mixed, strong and durable when hardened. These qualities explain why one material, concrete, can build skyscrapers, bridges, sidewalks and superhighways, houses, and dams. The character of the concrete is determined by the quality of the paste. Creep and shrinkage of concrete specimens occur during the loss and gain of water from cement paste. To better understand the role of water in mature concrete, a series of quasielastic neutron scattering (QENS) experiments were carried out on cement pastes with water/cement ratio varying between 0.32 and 0.6. The samples were cured for about 28 days in sealed containers so that the initial water content would not change. These experiments were carried out with an actual sample of Portland cement rather than with the components of cement studied by other workers. The QENS spectra differentiated between three different water interactions: water that was chemically bound into the cement paste, the physically bound or "glassy water" that interacted with the surface of the gel pores in the paste, and unbound water molecules that are confined within the larger capillary pores of cement paste. The dynamics of the "glassy" and "unboud" water in an extended time scale, from a hundred picoseconds to a few nanoseconds, could be clearly differentiated from the data. While the observed motions on the picosecond time scale are mainly stochastic reorientations of the water molecules, the dynamics observed on the nanosecond range can be attributed to long-range diffusion. Diffusive motion was characterized by diffusion constants in the range of (0.6-2) 10(-9) m(2)/s, with significant reduction compared to the rate of diffusion for bulk water. This reduction of the water diffusion is discussed in terms of the interaction of the water with the calcium silicate gel and the ions present in the pore water.     

Cracks and pores – Their roles in the transmission of water confined in cementitious materials

Cement paste is formed through a process called hydration by combining water with a cementitious material. Concrete, the worlds most versatile and most widely used material, can then be obtained when aggregates (sand, gravel, crushed stone) are added to the paste. The quality of hardened concrete is greatly influenced by the water confined in the cementitious materials and how it is transmitted through cracks and pores. Here we demonstrate that the water transport in cracks and capillary pores of hardened cement pastes can be approximately modeled by simple equations. Our findings highlight the significance of arresting the development of cracks in cementitious materials used in repository barriers. We also show that neutron scattering is an advantageous technique for understanding how water transmission is effected by gel pore structures. Defining measurable differences in gel pores may hold a key to prediction of the reduction of water transport through cement barriers.     

Rotational motion of the water molecules in the superconductor Na0.28CoO$_{\mathsf{2}} \!\cdot \!{\sf y}$H2O

Quasielastic neutron scattering (QENS) has been used to investigate the dynamical behaviour of H₂O in the superconductor Na_0.28CoO₂ .yH₂O. The measurements were obtained at room temperature for a molar concentration of water, y = 1.3. From the analysis of the Q-dependence of the EISF and the line-width we found that the water dynamics can be well described by rotational motion that likely correspond to re-orientation of the H₂O molecule. We were also able to define a rotational correlation time of τ= 1.85 ps.     

Quasi-elastic neutron scattering study of dimethyl-sulfoxide-water mixtures: probing molecular mobility in a nonideal solution

The translational and rotational motions of water and dimethyl sulfoxide, [DMSO, (CH(3))(2)SO] have been investigated using quasi-elastic neutron scattering. Water-DMSO mixtures at five DMSO mole fractions, chi(DMSO), ranging from 0 to 0.75, were measured. Hydrogen-deuterium substitution was used to extract independently the water proton dynamics (d-DMSO-H(2)O), the DMSO methyl proton dynamics (h-DMSO-D(2)O) and to obtain background corrections (d-DMSO-D(2)O). The translational diffusion of water slows down significantly compared to bulk water at all chi(DMSO)>0. The rotational time constant for water exhibits a maximum at chi(DMSO)=0.33 that corresponds to the observed maximum of the viscosity of the mixture. Data for DMSO can be analyzed in terms of a relatively slow tumbling of the molecule about its center-of-mass in conjunction with random translational diffusion. The rotational time constant for this motion exhibits some dependence on chi(DMSO), while the translational diffusion constant shows no clear variation for chi(DMSO)>0. The results presented reinforce the idea that due to the stronger associative nature of DMSO, DMSO-water aggregates are formed over the whole composition range, disturbing the tetrahedral natural arrangement of the water molecules. As a consequence adding DMSO to water causes a drastic slowing down of the dynamics of the water molecule, and vice versa.     

Looking at hydrogen motions in confinement

Why in a barren and hot desert, clays can contain a significant fraction of water? Why does concrete crack? How can we demonstrate that complexation of a drug does not alter its conformation in a way that affects its functionality? In this paper we present results on various studies using Quasi-Elastic Neutron Scattering aimed at clarifying these questions. To allow for a better understanding of neutron scattering, a brief introduction to the basics of its theory is presented. Following the theoretical part, experimental results dealing with the effects of confinement on the water dynamics caused by the interfaces in clays and the nano- and micro-pores of concrete are reviewed in detail. At the end, recent Quasi-Elastic Neutron Scattering investigations on the complexation of the local anesthetics Bupivacaine (BVC.HCl, C₁₈H₂₈N₂₀.HCl.H₂O) and Ropivacaine (RVC.HCl, C₁₇H₂₆N₂₀.HCl.H₂O) into the cyclic β-cyclodextrin oligosaccharide are presented. To conclude, the perspectives that the European Spallation Source brings to this subject are discussed.