Small angle X-ray scattering measurements probe water nanodroplet evolution under highly non-equilibrium conditions

Our in situ small angle X-ray scattering (SAXS) measurements yield an unprecedented and detailed view of rapidly evolving H(2)O nanodroplets formed in supersonic nozzles. The SAXS experiments produce spectra in a few seconds that are comparable to small angle neutron scattering (SANS) spectra requiring several hours of integration time and the use of deuterated compounds. These measurements now make it possible to quantitatively determine the maximum nucleation and growth rates of small droplets formed under conditions that are far from equilibrium. Particle growth is directly followed from about 10 micros to 100 micros after particle formation with growth rates of approximately 0.2 to 0.02 nm micros(-1). The peak H(2)O nucleation rates lie between 10(17) and 10(18) cm(-3) s(-1).     

Freezing water in no-man's land

We report homogeneous ice nucleation rates between 202 K and 215 K, thereby reducing the measurement gap that previously existed between 203 K and 228 K. These temperatures are significantly below the homogenous freezing limit, T(H)≈ 235 K for bulk water, and well within no-man's land. The ice nucleation rates are determined by characterizing nanodroplets with radii between 3.2 and 5.8 nm produced in a supersonic nozzle using three techniques: (1) pressure trace measurements to determine the properties of the flow as well as the temperature and velocity of the droplets, (2) small angle X-ray scattering (SAXS) to measure the size and number density of the droplets, and (3) Fourier Transform Infrared (FTIR) spectroscopy to follow the liquid to solid phase transition. Assuming that nucleation occurs throughout the droplet volume, the measured ice nucleation rates J(ice,V) are on the order of 10(23) cm(-3) s(-1), and agree well with published values near 203 K.     

Structure and dynamics of halogenoethanol-water mixtures studied by large-angle X-ray scattering, small-angle neutron scattering, and NMR relaxation

To clarify the structure of solvent clusters formed in halogenoethanol-water mixtures at the molecular level, large-angle X-ray scattering (LAXS) measurements have been made at 298 K on 2,2,2-trifluoroethanol (TFE), 2,2,2-trichloroethanol (TCE), and their aqueous mixtures in the TFE and TCE mole fraction ranges of 0.002 < or = x(TFE) < or = 0.9 and 0.5 < or = x(TCE) < or = 0.9, respectively. The radial distribution functions (RDFs) for TFE-water mixtures have shown that the structural transition from inherent TFE structure to the tetrahedral-like structure of water takes place at x(TFE) approximately 0.2. In the TCE-water mixtures inherent TCE structure remains in the range of 0.5 < or = x(TCE) < or = 1. Small-angle neutron scattering (SANS) experiments have been performed on CF(3)CH(2)OD- (TFE-d(1)-) D(2)O and CF(3)CD(2)OH- (TFE-d(2)-) H(2)O mixtures in the TFE mole fraction range of 0.05 < or = x(TFE) < or = 0.8. The SANS results in terms of the Ornstein-Zernike correlation length have revealed that TFE and water molecules are most heterogeneously mixed with each other in the TFE-water mixture at x(TFE) approximately 0.15, i.e., both TFE clusters and water clusters are most enhanced in the mixture. To evaluate the dynamics of TFE and ethanol (EtOH) molecules in TFE-water and ethanol-water mixtures, respectively, (1)H NMR relaxation rates for the methylene group within alcohol molecules have been measured by using an inversion-recovery method. The alcohol concentration dependence of the relaxation rates for the TFE-water and ethanol-water mixtures has shown a break point at x(TFE) approximately 0.15 and x(EtOH) approximately 0.2, respectively, where the structural transition from alcohol clusters to the tetrahedral-like structure of water takes place. On the basis of the present results, the most likely structure models of solvent clusters predominantly formed in TFE-water and TCE-water mixtures are proposed. In addition, effects of halogenation of the hydrophobic groups on clustering of alcohol molecules are discussed from the present results, together with the previous ones for ethanol-water and 1,1,1,3,3,3-hexafluoro-2-propanol- (HFIP-) water mixtures.     

Density measurement of 1-d confined water by small angle neutron scattering method: pore size and hydration level dependences

Small angle neutron scattering (SANS) is used to measure the absolute density of water contained in 1-D cylindrical pores of a silica material MCM-41-S with pore diameters of 19 and 15 A. By being able to suppress the homogeneous nucleation process inside the narrow pore, one can keep water in the liquid state down to at least 160 K. From a combined analysis of SANS data from both H(2)O and D(2)O hydrated samples, we determined the absolute value of the density of 1-D confined water. We found that the average density of water inside the fully hydrated 19 A pore is 8% higher than that of the bulk water at room temperature. The temperature derivative of the density shows a pronounced peak at T(L) = 235 K signaling the crossing of the Widom line at ambient pressure and confirming the existence of a liquid-liquid phase transition at an elevated pressure. Pore size and hydration level dependences of the density are also studied.     

Detection of homogeneous distribution of functional groups in mesoporous silica by small angle neutron scattering and in situ adsorption of nitrogen or water

The distribution of SO(3)H-functional groups attached to the ordered inner pore walls of mesoporous Si-MCM-41 materials based on SiO(2) was investigated by gas adsorption combined with in situ small angle neutron scattering (SANS). The functionalization was performed by two different methods, (i) grafting and (ii) co-condensation. The adsorbates N(2) at 77 K or a H(2)O/D(2)O mixture of 42:58 at 298 K possess neutron scattering length densities (SLD) similar to that of SiO(2) and therefore quench the diffraction signals of the nonmodified silica. SANS measurements show that N(2) matches completely not only with the pristine mesoporous Si-MCM-41 but also with Si-MCM-41-SO(3)H functionalized by grafting. Thus, full access of adsorbate into the entire length of the pores is proven. For the analysis of the distribution of functional groups within the pores in dependence on the used functionalization method, grafting or co-condensation, however, the more specific adsorbate H(2)O/D(2)O (42:58) is necessary, because it reacts more sensitively toward small changes in the SLD of the host material. For grafted Si-MCM-41-SO(3)H materials, an incomplete quenching was observed, indicating that only some regions, probably the pore mouths, have been modified. For a sample functionalized by co-condensation, almost no quenching of the neutron diffraction was found, indicating a very homogeneous distribution of the functional groups along the entire pores.     

Water distributions in polystyrene-block-poly[styrene-g-poly(ethylene oxide)] block grafted copolymer system in aqueous solutions revealed by contrast variation small angle neutron scattering study

We develop an experimental approach to analyze the water distribution around a core-shell micelle formed by polystyrene-block-poly[styrene-g-poly(ethylene oxide (PEO)] block copolymers in aqueous media at a fixed polymeric concentration of 10 mg/ml through contrast variation small angle neutron scattering (SANS) study. Through varying the D(2)O/H(2)O ratio, the scattering contributions from the water molecules and the micellar constituent components can be determined. Based on the commonly used core-shell model, a theoretical coherent scattering cross section incorporating the effect of water penetration is developed and used to analyze the SANS I(Q). We have successfully quantified the intramicellar water distribution and found that the overall micellar hydration level increases with the increase in the molecular weight of hydrophilic PEO side chains. Our work presents a practical experimental means for evaluating the intramacromolecular solvent distributions of general soft matter systems.     

Influence of nanoparticle addition on the properties of wormlike micellar solutions

The addition of positively charged, 30 nm diameter silica nanoparticles to cationic wormlike micellar solutions of cetyltrimethylammonium bromide and sodium nitrate is studied using a combination of rheology, small angle neutron scattering, dynamic light scattering, and cryo-transmission electron microscopy. The mixtures are single phase up to particle volume fractions of 1%. The addition of like-charged particles significantly increases the wormlike micelle (WLM) solution's zero shear rate viscosity, longest relaxation time, and storage modulus. The changes are hypothesized to originate from a close association of the particles with the micellar mesh. Small angle neutron scattering measurements with contrast matching demonstrate associations between particles mitigated by the WLMs. The effective interparticle interactions measured by SANS can explain the observed phase behavior. Dynamic light scattering measurements confirm the dynamic coupling of the particles to the micellar mesh.     

Tunable diode laser absorption spectroscopy study of CH(3)CH(2)ODD(2)O binary condensation in a supersonic Laval nozzle

We have developed a dual-beam tunable diode laser absorption spectroscopy system to follow the cocondensation of water and ethanol in a supersonic Laval nozzle. We determine the D(2)O monomer concentration in the vapor phase by fitting a Voigt profile to the measured line shape but had to develop a calibration scheme to evaluate the C(2)H(5)OD monomer concentration. To measure the temperature of the gas, we seed the flow with CH(4) and measure two absorption lines with different lower state energies. These data give a far more detailed picture of binary condensation than axially resolved pressure measurements. In particular, we observe that the C(2)H(5)OD monomer starts to be depleted from the gas phase well before D(2)O begins to condense.     

Soft fluctuating surfactant membranes in supercritical CO2-microemulsions

The bending rigidity of surfactant membranes in novel bicontinuous CO(2)-microemulsions of the type H(2)O/NaCl-scCO(2)-Zonyl FSH/Zonyl FSN 100 was determined using both high pressure small angle neutron scattering and neutron-spin echo spectroscopy. As an important result it was found, that the stiffness of the membrane increases solely by an increase of the pressure.     

Enrichment of deuterium oxide at hydrophilic interfaces in aqueous solutions

The structure of water at aqueous interfaces is of the utmost importance in biology, chemistry, and geology. We use neutron reflectivity and quartz crystal microbalance to probe an interface between hydrophilic quartz and bulk liquid solutions of H2O/D2O mixtures. We find that near the interface the neutron scattering length density is larger than in the bulk solution and there is an excess adsorbed mass. We interpret this as showing that there is a region adjacent to the quartz that is enriched in D2O and extends 5-10 nm into the solution. This suggests caution when interpreting results where D2O is substituted for H2O in aqueous interfacial chemistry.     

Structural requirements and reaction pathways in dimethyl ether combustion catalyzed by supported Pt clusters

The identity and reversibility of the elementary steps required for catalytic combustion of dimethyl ether (DME) on Pt clusters were determined by combining isotopic and kinetic analyses with density functional theory estimates of reaction energies and activation barriers to probe the lowest energy paths. Reaction rates are limited by C-H bond activation in DME molecules adsorbed on surfaces of Pt clusters containing chemisorbed oxygen atoms at near-saturation coverages. Reaction energies and activation barriers for C-H bond activation in DME to form methoxymethyl and hydroxyl surface intermediates show that this step is more favorable than the activation of C-O bonds to form two methoxides, consistent with measured rates and kinetic isotope effects. This kinetic preference is driven by the greater stability of the CH3OCH2* and OH* intermediates relative to chemisorbed methoxides. Experimental activation barriers on Pt clusters agree with density functional theory (DFT)-derived barriers on oxygen-covered Pt(111). Measured DME turnover rates increased with increasing DME pressure, but decreased as the O2 pressure increased, because vacancies (*) on Pt surfaces nearly saturated with chemisorbed oxygen are required for DME chemisorption. DFT calculations show that although these surface vacancies are required, higher oxygen coverages lead to lower C-H activation barriers, because the basicity of oxygen adatoms increases with coverage and they become more effective in hydrogen abstraction from DME. Water inhibits reaction rates via quasi-equilibrated adsorption on vacancy sites, consistent with DFT results indicating that water binds more strongly than DME on vacancies. These conclusions are consistent with the measured kinetic response of combustion rates to DME, O2, and H2O, with H/D kinetic isotope effects, and with the absence of isotopic scrambling in reactants containing isotopic mixtures of 18O2-16O2 or 12CH3O12CH3-13CH3O13CH3. Turnover rates increased with Pt cluster size, because small clusters, with more coordinatively unsaturated surface atoms, bind oxygen atoms more strongly than larger clusters and exhibit lower steady-state vacancy concentrations and a consequently smaller number of adsorbed DME intermediates involved in kinetically relevant steps. These effects of cluster size and metal-oxygen bond energies on reactivity are ubiquitous in oxidation reactions requiring vacancies on surfaces nearly saturated with intermediates derived from O2.     

Alpha,alpha-trehalose-water solutions. VIII. Study of the diffusive dynamics of water by high-resolution quasi elastic neutron scattering

The present paper shows high-resolution quasi-elastic neutron scattering (QENS) findings on homologues disaccharides (i.e. trehalose, maltose, and sucrose)-water mixtures as a function of temperature. The QENS measurements were performed on both partially deuterated disaccharides in D2O and on hydrogenated disaccharides in H2O to separate the solute dynamics from that of the solvent. The results highlight a noticeable disaccharide kosmotrope character, with results more marked for trehalose. Such evidence accounts for its higher bioprotective effectiveness.     

Distorted hexagonal phase studied by neutron diffraction: lipid components demixed in a bent monolayer

The recent discovery of a distorted hexagonal phase in 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine/1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPE/DOPC) mixtures raised the intriguing question as to whether lipid mixtures demix in a bent monolayer. We performed neutron diffraction on a mixture of headgroup deuterated DOPC-d(13) and nondeuterated DOPE to study the lipid distribution in the distorted hexagonal phase. The 1:1 lipid mixture in full hydration and 25 degrees C was in a homogeneous lamellar phase. Upon dehydration the mixture transformed to a rhombohedral phase, then to a distorted inverted hexagonal phase, and finally to a regular inverted hexagonal phase. In the distorted hexagonal phase, the diffraction pattern showed a two-dimensional monoclinic lattice with two reciprocal vectors of equal length (1.5 nm(-)(1)) forming an angle 53 degrees between them. Diffraction intensities measured while varying the D(2)O/H(2)O ratio in the humidity was used to solve the phase problem. The neutron scattering length density distribution of the distorted hexagonal phase was constructed. The constant density contours are approximately elliptical. The difference in the eccentricities of the contours between the water and lipid distributions indicates that the DOPE/DOPC ratio is not uniform around the elliptical lipid tube in the unit cell. DOPE is preferentially distributed at the vertex regions where the curvature is the highest. Thus for the first time it is shown that when a monolayer of a homogeneous lipid mixture is bent, the lipid components are partially demixed in reaching the free energy minimum.     

Water-barrier properties of mixed bis[trimethoxysilylpropyl]amine and vinyltriacetoxysilane films

X-ray and neutron reflectivity were employed to elucidate the morphologies of bis[trimethoxysilylpropyl]amine silane (A) and vinyltriacetoxysilane (V) mixed films on Si wafers at different A/V ratios, and the response of these films to saturated water vapor. Due to its insensitivity to chemical composition, X-ray reflectivity was used to assess the film density, whereas neutron reflectivity was used to probe water absorption and chemical change on exposure to water. NMR was employed to determine the reaction mechanism in neat AV mixtures and stoichiometry of the initial reaction. X-ray reflectivity reveals about 30% void volume in the films with the least void volume detected near stoichiometry. Grazing incidence small-angle scattering (GISAXS) shows that the void volume is at the molecular level, with no distinct pores. Neutron reflectivity on D2O-conditioned films shows that silane film is not an effective water barrier with about 30 vol % water being absorbed with only a slight thickness increase. Most water is physically absorbed in the void space with the least amount being absorbed near the stoichiometric A/V ratio. The scattering length density of the films almost returns to the virgin state after re-dry following D2O vapor exposure. The film thickness, however, remains at the water-vapor-conditioned state. The slight increase in scattering length density and irreversible thickness change after re-dry indicate some reaction with water during D2O conditioning. A D-rich layer is also observed at the air side surface in D2O-conditioned films regardless of A/V ratio.     

Protein aggregate structure under high pressure

We show that casein protein micelles--a complex protein/inorganic phosphate structure--can be subjected to high pressures (up to 350 MPa) while making in situ structural measurements using (ultra-)small angle neutron scattering, to give insight to the protein structure, aggregation and stability under pressure.     

Gas phase hyper-Rayleigh scattering measurements

Measurements of hyper-Rayleigh scattering intensities and polarization ratios are presented for nine small molecules in the gas phase [CH(4), CF(4), CCl(4), N(2)O, NH(3), D(2)O, SO(2), CF(2)Cl(2), and (CH(3))(2)CO]. In four cases [CH(4), CF(4), CCl(4), and N(2)O] all molecular hyperpolarizability tensor components can be determined from the measurements. The results of this experiment are compared with the results of previous ab initio calculations, finding discrepancies up to 60%. Including vibrational contributions decreases the discrepancies for CH(4) and CF(4) and increases them for CCl(4), D(2)O, and NH(3).     

Self-assembly of mixed anionic and nonionic surfactants in aqueous solution

We present the phase diagram and the microstructure of the binary surfactant mixture of AOT and C(12)E(4) in D(2)O as characterized by surface tension and small angle neutron scattering. The micellar region is considerably extended in composition and concentration compared to that observed for the pure surfactant systems, and two types of aggregates are formed. Spherical micelles are present for AOT-rich composition, whereas cylindrical micelles with a mean length between 80 and 300 ? are present in the nonionic-rich region. The size of the micelles depends on both concentration and molar ratio of the surfactant mixtures. At higher concentration, a swollen lamellar phase is formed, where electrostatic repulsions dominate over the Helfrich interaction in the mixed bilayers. At intermediate concentrations, a mixed micellar/lamellar phase exists.     

Surface-induced unfolding of human lactoferrin

We have determined the structural conformations of human lactoferrin adsorbed at the air/water interface by neutron reflectivity (NR) and its solution structure by small angle neutron scattering (SANS). The neutron reflectivity measurements revealed a strong structural unfolding of the molecule when adsorbed at the interface from a pH 7 phosphate buffer solution (PBS with a total ionic strength at 4.5 mM) over a wide concentration range. Two distinct regions, a top dense layer of 15-20 angstroms on the air side and a bottom diffuse layer of some 50 angstroms into the aqueous subphase, characterized the unfolded interfacial layer. At a concentration around 1 g dm(-3), close to the physiological concentration of lactoferrin in biological fluids, the adsorbed amount was 5.5 x 10(-8) mol m(-2) in the absence of NaCl, but the addition of 0.3 M NaCl reduced protein adsorption to 3.5 x 10(-8) mol m(-2). Although the polypeptide distributions at the interface remained similar, quantitative analysis showed that the addition of NaCl reduced the layer thickness. Parallel measurements of lactoferrin adsorption in D2O instead of null reflecting water confirmed the unfolded structure at the interface. Furthermore, the D2O data indicated that the polypeptide in the top layer was predominantly protruded out of water, consistent with it being hydrophobic. In contrast, the scattering intensity profiles from SANS were well described by a cylindrical model with a diameter of 47 angstroms and a length of 105 angstroms in the presence of 0.3 M NaCl, indicating a retention of the globular framework in the bulk solution. In the absence of NaCl but with the same amount of phosphate buffer, the length of the cylinder increased to some 190 angstroms and the diameter remained constant. The length increase is indicative of changes in distance and orientation between the bilobal monomers due to the change in charge interactions. The results thus demonstrate that the surface structural unfolding was caused by the exposure of the protein molecule to the unsymmetrical energetic balance following surface adsorption.     

Interactions between block copolymers and single-walled carbon nanotubes in aqueous solutions: a small-angle neutron scattering study

The amphiphilic copolymers of the Pluronic family are known to be excellent dispersants for single-walled carbon nanotubes (SWCNT) in water, especially F108 and F127, which have rather long end-blocks of poly(ethylene oxide) (PEO). In this study, the structure of the CNT/polymer hybrid formed in water is evaluated by measurements of small-angle neutron scattering (SANS) with contrast variation, as supported by cryo-transmission electron microscopy (cryo-TEM) imaging. The homogeneous, stable, inklike dispersions exhibited very small isolated bundles of carbon nanotubes in cryo-TEM images. SANS experiments were conducted at different D(2)O/H(2)O content of the dispersing solvent. The data for both systems showed surprisingly minimal intensity values at 70% D(2)O solvent composition, which is much higher than the expected value of 17% D(2)O that is based on the scattering length density (SLD) of PEO. At this near match point, the data exhibited a q(-1) power law relation of intensity to the scattering vector (q), indicating rodlike entities. Two models are evaluated, as extensions to Pederson's block copolymer micelles models. One is loosely adsorbed polymer chains on a rodlike CNT bundle. In the other, the hydrophobic block is considered to form a continuous hydrated shell on the CNT surface, whereas the hydrophilic blocks emanate into the solvent. Both models were found to fit the experimental data reasonably well. The model fit required special considerations of the tight association of water molecules around PEO chains and slight isotopic selectivity.