Neutron scattering and compressibility measurements for the study of hydration effects on polymeric aqueous solutions

Summary The present paper reports the results of compressibility and incoherent quasi-elastic neutron scattering measurements performed on polymeric systems and on their aqueous solutions. From the compressibility data, the temperature evolution of the polymer hydration number can be derived. On the other hand, neutron data show that the translational diffusion coefficientD _T turns out to be higher in the case of ethylene glycol + water, with respect to that of pure, suggesting that the water molecules act as a ?structure breaker? of the intermolecular connectivity existing into the pure. Furthermore the dynamical properties of the H₂O molecules in the presence of poly(ethylene glycol) deeply differ from those in the bulk, and show that we are in the presence of entangled water. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Excess water dynamics in hydrotalcite: QENS study

Results of the quasi-elastic neutron scattering (QENS) measurements on the dynamics of excess water in hydrotalcite sample with varied content of excess water are reported. Translational motion of excess water can be best described by random translational jump diffusion model. The observed increase in translational diffusivity with increase in the amount of excess water is attributed to the change in binding of the water molecules to the host layer.     

Association of rhodamine 6G in light and heavy water solutions

The absorption characteristics of rhodamine 6G molecules in light and heavy water solutions are studied. The association efficiencies of dye molecules and the structure and the binding energy of complexes formed are determined in relation to the solvent composition. The structure of H₂O +D₂O solutions is studied using correlation and low-frequency Raman spectroscopy. The distribution of dissolved complex molecules in the water matrix is shown to have inhomogeneities, which are responsible for a high association efficiency. The characteristic size of these inhomogeneities is estimated. The fractal dimension of the structural formations of light and heavy water molecules is determined as a function of their concentration.     

Effect of chemical binding energy on the dynamics of water

The calculated value of γ₁₁, a neutron-condensed system energy observable, using the recent neutron scattering kernel proposed by the authors which incorporates explicitly chemical binding amongst the water molecules, turns out to be in much better agreement with the experimental result than that given by the widely used Nelkin kernel. Low energy collective oscillations, thus, play an important role in the dynamics of water.     

Experimental investigation of C60/NMP/toluene solutions by UV-Vis spectroscopy and small-angle neutron scattering

The transformation of the C₆₀ fullerene cluster state into C₆₀/N-methylpyrrolidone (NMP) solution after the addition of a nonpolar solvent (toluene, electric permittivity ?= 2.4) is studied. The results of ultraviolet-visible spectroscopy and small-angle neutron scattering measurements are used for comparison of the C₆₀/NMP/toluene system with C₆₀/NMP mixtures with a high-polar solvent (water, ? = 80). As to the observed reorganization of the cluster state, the C₆₀/NMP/toluene system is similar to the C₆₀/NMP/water system. This effect is explained by the formation of charge-transfer complexes in the initial C₆₀/NMP solution. These complexes are thought to be soluble in both binary mixtures. The connection between the cluster-reorganization effect and solvatochromism is discussed.     

Effect of X-ray energies on induced photo-neutron doses

Photoneutrons induced by two high energies range from the Elekta medical linear accelerator (10 and 18 MV) were measured by nuclear track detectors (NTDs). CR-39 NTD in contact with converter screen slide films, natural boron of thickness 40 μm coated on the polyester film (BN1). Detectors were exposed at 100 cm SSD with field size 20×20 on the patient table, with chest phantom and with build-up Perspex used for high-energy exposure. CR-39 registers the thermal neutron by the (n–α) reaction with the thin layer of boron and the fast neutron was measured through the (n–p) elastic scattering with the H₂ molecules in the CR-39 constituents.It was found that the total neutron dose (thermal and fast) from the 18 MV X-ray is higher than that of 10 MV. The measured thermal neutron dose is relatively smaller than the fast neutron dose in the case of direct exposure at the two X-ray energies. On the other hand, in the case of measurements on phantom and upon the use of build-up Perspex sheets, the ratio of fast to that of thermal is less than that of direct exposure.     

Dynamics of water molecules adsorbed by silica and resin SGK-7

This paper has presented neutron spectroscopy data on the dynamics of light water molecules adsorbed in the cation exchanger (ion-exchange resin) SGK-7 and on the surface of aerosils (highly dispersed pyrogenic silica) with different levels of hydration. The measurements have been performed on a DIN-2PI spectrometer (Frank Laboratory of Neutron Physics of the Joint Institute for Nuclear Research, Dubna, Russia). The characteristics of the diffusive and vibrational motions of adsorbed water molecules have been determined from the experimental neutron scattering spectra. The data obtained in the quasi-elastic neutron scattering region have been analyzed using a model accounting for the effects of restricted translational and rotational diffusion. The results have demonstrated a significant decrease in the diffusion mobility of adsorbed water molecules as compared to conventional (bulk) water. In particular, the self-diffusion coefficient decreases several times, and the diffusion rate is the lower, the smaller is the thickness of the hydration layer. The dependences of the intensity and half-width of the quasi-elastic scattering peak on the magnitude of the neutron momentum transfer q in the scattering process exhibit a nonmonotonic character. This indicates manifestation of the effects of restricted translational diffusion, rotational diffusion, and jump diffusion. The partial distributions of vibrational frequencies of hydrogen atoms of water molecules adsorbed by the cation exchanger and aerosils have been obtained from the inelastic neutron scattering data.     

Interactions of triiodide cluster ion with solvents

An equilibrium molecular dynamics model is developed to investigate the interactions of triiodide cluster ion with solvents. The internal dynamics of the triiodide ion is described by a valence bond model which responds to the field of the classical solvent molecules. The solvent molecules were described by standard classical models with rigid molecules, fixed partial charges on atomic sites and site-site Lennard-Jones interactions. One finds the solvent effects on the I^-₃ are unusually strong as it is a very polarizable species. Protic solvents such as water, ethanol, and methanol that can form hydrogen bonds to lead to the I^-₃ geometry with two unequal bonds and an asymmetric distribution of charges. But for the solvents such as xenon, tetrahydrofuran, methyltetrahydrofuran, and acetonitrile, the I^-₃ only illustrates a geometry with two equal bonds. We find that structure changing is induced by local electrostatic attraction between solvent molecules.     

Effect of water–methanol content on the structure of Nafion in the sandwich model and solvent dynamics in nano-channels; a molecular dynamics study

Continuing an ongoing study, molecular dynamics (MD) simulations were performed to investigate the effects of methanol concentration on Nafion morphology, such as the size of solvent cluster, solvent location, and polymer structure via the sandwich model. Our survey shows that high methanol concentrations resulted in increment of solvent cluster size in Nafion membrane. The sulfonic acid clusters also befall much in order as subsequent layers of such ionic clusters are formed. The number of neighbouring hydronium ions around a sulfur atom is independent of methanol concentration, but the first shell of hydronium and water around sulfonic acid clusters is broader. Although methanol would prefer to interact with water molecules rather than sulfonic acid groups, gathering of methanol molecules via hydrophobic self-aggregation is preferred. Methanol is located closer to the hydrophobic part of the polymer than water, while water is located closer to the hydrophilic part of the polymer. It was found that methanol distributes specifically more than water in nano-channels. Investigation of solvent dynamics in nano-channels shows that diffusion coefficients (D) of water, methanol, and hydronium decrease with increasing methanol concentration and they may be ordered as follows: D _Water?>?D _Methanol?>?D _Hydronium (D _Water?≈?1.6–2.0D _Methanol and D _Methanol?≈?2.1–3.0D _Hydronium).     

NMR study of defect and stoichiometric water molecules in K2Pt(CN)4Br0.33.2H2O (KCP)

By nuclear magnetic resonance we have confirmed in KCP the existence of a third water position. It is occupied by a “defect” water molecule with a high degree of positional disorder most likely due to a space distribution over at least 16 different orientations. The stoichiometric water molecules in the H₂O (1) site are ordered, while those of the H₂O (2) site are dynamically disordered. These results are discussed in terms of recent X-ray and neutron diffraction experiments.     

Use of Terbium(III) as a Probe for the Ion-Binding Properties of Tactic Polyacids and Triacidic Model Compounds

The binding properties of Tb(III) ions in configurationally different environments were investigated using luminescence intensity and lifetime measurements. The emission intensity of Tb(III) (⁵D₄–⁷F₅ transition) is directly dependent upon the number of coordinated water molecules (quenchers) bound in the inner coordination sphere. The more efficiently a ligand coordinates to Tb(III) ion, the more water molecules are expelled from the coordination sphere, thereby enhancing the luminescence intensity and lifetime of the ion. Isotactic and syndiotactic poly(methacrylic acids) (PMAs) were neutralized and complexed with Tb(III) ions in aqueous solutions. The luminescence intensities and lifetimes were monitored with _exc = 265, the hypersensitive excitation band at 286 and 370 nm. The isotactic PMA/Tb(III) complex exhibited a six times greater luminescence intensity than the syndiotactic PMA complex. Lifetime measurements showed 2.4 water molecules coordinated to Tb(III) ion in the isotactic PMA complex, while 3.4 water molecules were found to remain in the syndiotactic complex. Similar studies were also conducted on small organic model compounds such as Kemp's triacid and its configurational isomer. These data supported the polymeric results where the isotactic model, Kemp's triacid, exhibited a higher luminescence intensity and a longer lifetime than the Kemp's isomer. Lifetime results showed the Kemp's molecule retained approximately 2.7 water molecules, compared to four water molecules for the isomer. The validity of using the Kemp's molecules as polymeric models is also discussed.     

Molecular dynamics simulations of a mixed DOPC/DOPG bilayer

We have constructed a mixed dioleoylphosphatidylcholine (DOPC) and dioleoylphosphatidylglycerol bilayer (DOPG) bilayer utilizing MD simulations. The aim was to develop an explicit molecular model of biological membranes as a complementary technique to neutron diffraction studies that are well established within the group. A monolayer was constructed by taking a previously customized PDB file of each molecule and arranging them in a seven rows of ten molecules and duplicated and rotated to form a bilayer. The 140-molecule bilayer contained 98 DOPC molecules and 42 DOPG molecules, in a 7:3 ratio in favour of DOPC. Sodium counter ions were placed near the phosphate moiety of DOPG to counteract the negative charge of DOPG. This was representative of the lipid ratio in a sample used for neutron diffraction. The MD package GROMACS was used for confining the bilayer in a triclinic box, adding Simple Polar Charge water molecules, energy minimization (EM). The bilayer/solvent system was subjected to EM using the steepest descent method to nullify bad contacts and reduce the potential energy of the system. Subsequent MD simulation using an initial NVT (constant number of particles, volume and temperature) for a 20 ps MD run followed by a NPT (constant number of particles, pressure and temperature) was performed. Structural parameters including volume of lipid, area of lipid, order parameter of the fatty acyl carbons and electron density profiles generated by the MD simulation were verified with values obtained from experimental data of DOPC, as there are no comparable experimental data available for the mixed bilayer.     

Ab initio molecular dynamics investigations of structural, electronic and dynamical properties of water in supercritical carbon dioxide

Ab initio molecular dynamics simulations of a solitary perdeuterated water molecule solvated in supercritical carbon dioxide have been performed along an isotherm at three different densities. Electron donor-acceptor interactions between the oxygen atom of water and the carbon atom of CO₂ as well as hydrogen bonded interactions between the two molecules have been shown to play a dominant role in the solvation. The mean dipole moment of the water molecule increases with the density of the solution, from a value of 1.85 D at low density to around 2.15 D at the highest density. The increase in the solvent density causes the water molecule to exhibit a range of behavior, from a free molecule to one that interacts strongly with CO₂. A blue shift in the bending mode of water has been observed with increasing solvent density. The carbon dioxide molecules which are present in the first neighbor shell of water are found to exhibit larger propensity to deviate from a linear geometry in their instantaneous configurations.      

Sodium affinity of caffeine and adenine: the effect of microsolvation and electrostatic field of solvent on the sodium affinity

The sodium affinity (SA) of caffeine (CAF), adenine (AD) and their microsolvated clusters containing one X molecule (CAF-X and AD-X; X = H₂O, NH₃, H₂S and HF) has been calculated in the gas phase and water, separately. The density functional theory (DFT) employing CAM-B3LYP functional has been used for all of the calculations in this work. The solvent was modelled by the polarised continuum model (PCM) which considers the electrostatic field of solvent on solute. The calculated SA of [CAF-X] and [AD-X] was higher than that of CAF and AD in the gas phase, respectively, which showed that the microsolvation of molecules in the gas phase could be used for changing the tendency of molecules for binding to Na⁺. Also, it was observed that the electrostatic effect of solvent decreases the SA of the species compared to the gas phase, considerably. The symmetry adapted perturbation theory (SAPT) calculations were also used to interpret the change in the SA of CAF and AD due to the clustering with one X molecule in the gas phase. In addition, there is a detailed study on the position of Na⁺ relative to AD and CAF structures in different conditions including gas phase, microsolvation and electrostatic field of solvent in this work.     

Quasi-elastic neutron scattering study of AlCl3 aqueous solution

Quasi-elastic neutron scattering from protons in AlCl₃ aqueous solution has been measured by the use of a triple-axis spectrometer. Assuming the existence of two different kinds of water molecules, either in free state or in bound state, the whole shape of energy spectra of scattered neutrons was analyzed. About eight water molecules were found to be bound to an Al ion, being almost independent of the solute concentration. The diffusion constant, the rest time and the jump length of the remaining free water molecules were estimated based on a jump diffusion model.     

The neutron spin phase imaging technique applied to dia- and paramagnetic samples

We report on a novel application of the Neutron Spin Phase Imaging technique, by performing polarised neutron radiography on dia- and paramagnetic samples. In order to achieve the necessary sensitivity we employed a 2.5 T Ramsey apparatus which was used in a previous experiment to measure the spin-dependent neutron scattering length of the deuteron. First successful results on aluminium, lead, titanium and heavy water (D₂O) samples are presented. They are in good quantitative agreement with expected values deduced from susceptibility measurements.     

Effect of iron doping on the hydrophobicity of titanium dioxide film: experiment and simulation

In this study, we carried out experiments and molecular dynamics simulations to identify the effect of Fe doping on the hydrophobicity of a titanium dioxide film. TiO₂ and Fe-doped TiO₂ films were fabricated in situ by atomic layer deposition without annealing. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterise the crystal structure and elemental composition. Iron doping resulted in the TiO₂ becoming more hydrophobic at a macroscopic level, as estimated by atomic force microscopy observations and static contact angle measurements. Furthermore, the effect of iron doping on the structure and kinetics of water molecules on the exterior of TiO₂ were studied by molecular dynamics simulations. On the basis of the XPS results, the Fe-TiO₂ surface matrix has a Ti:Fe ratio of 36:5. In addition, the density distribution of oxygen and hydrogen atoms indicate that interfacial water molecules enter the Fe-TiO₂ film more easily and hydrogen atoms in the water molecules are oriented upward at the interface. The self-diffusion coefficients indicate that iron doping makes the TiO₂ more hydrophobic, which is consistent with the macroscopic test results.     

Structure of amyloid aggregates of lysozyme from small-angle X-ray scattering data

The structure of filament amyloid aggregates of hen egg white lysozyme in water has been investigated by the small-angle X-ray scattering method. The experimental data are described by different cylindrical models, among which the best agreement is reached with the long helix model. A comparison of the results with the small-angle neutron scattering data reveals the influence of the heavy component of the solvent (a H₂O/D₂O mixture) on the structure of the filaments.     

Investigation of Solvent Effects on Photophysical Properties of New Aminophthalimide Derivatives-Based on Methanesulfonate

Novel aminophthalimide derivatives were synthesized starting from (3aR,7aS)-2-(2-hydroxypropyl)-3a,4,7,7a–tetrahydro-1H-isoindole-1,3(2H)-dione (9) , and solvent effects on the photo-physical properties of these newly synthesized aminophthalimide derivatives (compounds 14 and 15) were investigated using UV-Vis absorption spectroscopy, steady-state and time-resolved fluorescence measurements. Both absorption and fluorescence spectra exhibited bathochromic shift with the increased polarity of the solvents for both molecules. Solute-solvent interactions were analyzed using the Lippert-Mataga and Bakhshiev polarity functions, and Kamlet-Taft and Catalan multiple linear regression approaches. The results revealed that these two molecules experienced specific interactions. Furthermore, photo-physical parameters were calculated for both molecules in all of the solvents, such as the fluorescence quantum yield, fluorescence lifetime, radiative (k_r) and non-radiative (k_nr) rate constant values. It was observed that the fluorescence quantum yield values decreased linearly with increasing solvent polarity. This study proved the new dyes including isopropyl methanesulfonate group displayed different behavior from previous studies of aminophthalimide derivatives in water. It was recommended that these new dyes having interesting properties by changing solvent can be used various applications such as environmentally sensitive fluorescent probes, labels in biology, laser industry.     

Incoherent quasielastic neutron scattering from H2O and aqueous ZnCl2 solutions

A study of the diffusive motions of the protons in pure water and ZnCl₂ aqueous solutions has been performed, using incoherent quasielastic neutron scattering. It is shown that it is essential to take into account the rotational motion of the water molecules. The translational linewidth is conveniently fitted over the whole Q-range, using the Random Jump Diffusion model for which the jump length turns out to be roughly the same for pure H₂O and the saturated solution, fairly close to the distance between protons in the water molecule.