Small-angle neutron scattering studies of sodium butyl benzene sulfonate aggregates in aqueous solution

The aggregation behaviour of a hydrotrope, sodiumn-butyl benzene sulfonate (Na-NBBS), in aqueous solutions is investigated by small-angle neutron scattering (SANS). Nearly ellipsoidal aggregates of Na-NBBS at concentrations well above its minimum hydrotrope concentration were detected by SANS. The hydrotrope seems to form self-assemblies with aggregation number of 36–40 with a substantial charge on the aggregate. This aggregation number is weakly affected by the hydrotrope concentration.     

Rheological Behavior of Some Cationic Polyelectrolytes

The rheological behavior of some cationic polyelectrolytes in aqueous solution is presented. The polyelectrolytes under study consist of polycations that have positive charges (N,N-dimethyl-2-hydroxypropylenammonium chloride) located along the main chain with or without nonpolar side chains (PCA₅D₁ and PCA₅, respectively). This investigation mainly considers the influence of oscillation frequency and temperature on their rheological behavior in salt-free aqueous solution at three polymer concentrations (c_p = 2%, 4%, and 6%) as well as in the presence of low molar mass salt (NaCl). The results indicate the main effect of these parameters was to modify the hydrophobic interactions between the side nonpolar groups of the modified polyelectrolyte. The comparison between the complex viscosity values, at the same polymer concentration, c_p = 4%, for PCA₅D₁ and PCA₅ shows higher values in the whole interval of temperatures under study and a pseudoplastic behavior at temperatures greater than 50°C for the former system.     

SANS and light scattering of nonylammonium chloride micelles in aqueous solutions of sodium chloride

Summary Aqueous solutions of nonylammonium chloride (NAC) containing sodium chloride were studied by using light scattering and small-angle neutron scattering (SANS) techniques. It was found that the aggregation number of NAC is independent of the surfactant concentration and increases smoothly with increasing the ionic strength. Micelles of NAC in D₂O with [NaCl]=0.3422 have prolate ellipsoidal shape and their average aggregation number is greater than that found in H₂O at the same ionic strength. A possible explanation of this difference may arise from a solvent effect. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Synthesis and Investigation of Double Stimuli-Responsive Behavior of N-Isopropylacrylamide and Maleic Acid Copolymer in Solutions

Poly(N-isopropylacrylamide-co-maleic acid) [poly(NIPAAm-co-MA)] linear copolymer with comonomer molar ratio NIPAAm:MA = 94:6 was synthesized by free-radical copolymerization. The molar mass, M_sD = 28,000 Da, of poly(NIPAAm-co-MA) was determined using hydrodynamic methods. The self-assembly of poly(NIPAAm-co-MA) in aqueous solution at a concentration of 0.015 g cm^?3 within the pH interval from 1.8 to 10.6 and the temperature interval from 22 to 60°C was investigated by static and dynamic light scattering. The copolymer showed a double temperature and pH responsiveness. Three types of particles, namely, macromolecules (or unimers), micellar-like structures, and loose aggregates existed in the poly(NIPAAm-co-MA) aqueous solutions. The fraction of dissolved entities and the hydrodynamic radii of the micellar-like structures and loose aggregates depended considerably on temperature and pH. The temperature of the phase separation and the width of the phase separation interval increased with pH. An influence of pH on kinetic processes in poly(NIPAAm-co-MA) solutions was observed.     

Mobility of water in NaCl and brain heart infusion (BHI) solutions as studied by 17O NMR

The molecular dynamic behaviour of water molecules in aqueous solution has been determined by oxygen-17 NMR according to the anisotropic reorientation, two-correlation-time model for bound water. Solutions of brain heart infusion (BHI), NaCl and their 1:1 mixture have been analysed. The anisotropic water population was distinguished into a slow (τ^s _bw) and a fast (τ^f _bw) relaxing component. The slow relaxing component was affected by the nature of the solute, while the fast relaxing component was not. NaCl was found to bind water molecules more strongly (higher τ^s _bw) than BHI. Water was more bound in the 1:1 mixture than in the solution containing only BHI. The population of bound water (P _bw) was concentration dependent and increased with increasing solids content. BHI, at the suspension point, bound ～50% of the total water, while NaCl at saturation bound only ～10%. The 1:1 mixture bound water in a synergistic manner that resulted in a slightly higher P_bw, than in BHI at each solid concentration. The P_bw correlated well with the amount of unfreezable water (as measured by DSC) present in the BHI samples.     

Humic acid metal cation interaction studied by spectromicroscopy techniques in combination with quantum chemical calculations

Humic acids (HA) have a high binding capacity towards traces of toxic metal cations, thus affecting their transport in aquatic systems. Eu(III)–HA aggregates are studied by synchrotron‐based scanning transmission X‐ray microscopy (STXM) at the carbon K‐edge and laser scanning luminescence microscopy (LSLM) at the ⁵D₀→⁷F_1,2 fluorescence emission lines. Both methods provide the necessary spatial resolution in the sub‐micrometre range to resolve characteristic aggregate morphologies: optically dense zones embedded in a matrix of less dense material in STXM images correspond to areas with increased Eu(III) luminescence yield in the LSLM micrographs. In the C 1s‐NEXAFS of metal‐loaded polyacrylic acid (PAA), used as a HA model compound, a distinct complexation effect is identified. This effect is similar to trends observed in the dense fraction of HA/metal cation aggregates. The strongest complexation effect is observed for the Zr(IV)–HA/PAA system. This effect is confirmed by quantum chemical calculations performed at the ab initio level for model complexes with different metal centres and complex geometries. Without the high spatial resolution of STXM and LSLM and without the combination of molecular modelling with experimental results, the different zones indicating a `pseudo'‐phase separation into strong complexing domains and weaker complexing domains of HA would never have been identified. This type of strategy can be used to study metal interaction with other organic material.     

Structural changes during the unfolding of Bovine serum albumin in the presence of urea: A small-angle neutron scattering study

The native form of serum albumin is the most important soluble protein in the body plasma. In order to investigate the structural changes of Bovine serum albumin (BSA) during its unfolding in the presence of urea, a small-angle neutron scattering (SANS) study was performed. The scattering curves of dilute solutions of BSA with different concentrations of urea in D₂O at pH 7.2 ± 0.2 were measured at room temperature. The scattering profile was fitted to a prolate ellipsoidal shape (a, b, b) of the protein witha = 52.2 Å andb = 24.2 Å. The change in the dimensions of the protein as it unfolds was found to be anisotropic. The radius of gyration of the compact form of the protein in solution decreased as the urea concentration was increased.     

Effect of heavy-metal ions on dynamic characteristics of collagen molecules in solutions

Effect of heavy (Pb²⁺, Cs⁺) and light (Na⁺) metal ions on the molecular-dynamic characteristics of type-I collagen in aqueous solution was studied using the method of dynamic light scattering. It was found that the dependence of the translational diffusion coefficient D _t from pH solutions has a nonlinear form with a pronounced extremum close to the isoelectric point of the protein (pI 6.0). For pure aqueous solution of protein there is a maximum of D _t in isoelectric point. For collagen solutions with the addition of heavy-metal salts the minimum of D _t was observed near the isoelectric point. This fenomenon is connected with the formation of protein nanoclusters in solution. With concentration of heavy metal ions increasing translational diffusion coefficient Dt decreases, which shows on increasing of aggregation effect. The addition of sodium ions in aqueous solution of collagen containing heavy metal ions sharp decreasing of the translational diffusion of molecules is observed. That can be connected with the rise of scattering particles masses.     

Removal of aliphatic amino acids by hybrid organic-inorganic layered compounds

Amino acids have been extensively used in several processes of the pharmaceutical and food industries. Treatments for the recovery and reuse of the wastewaters generated from these processes are few and little known. This work aims at studying the influence of variables like temperature, pH and ionic strength on the adsorption of the amino acids Asp and Glu, contained in aqueous solutions, on layered double hydroxides of the Mg-Al-CO₃-LDH system. The adsorption experiments were performed at two different temperatures (298 and 310 K), two different pH values (7.0 and 10.0), and two ionic strength conditions (with or without the addition of NaCl). The adsorption isotherms exhibited similar profiles under the various conditions studied: an increase in temperature as well as an increase in the pH value decreased the amount of adsorbed amino acid while an increase in the ionic strength increased Asp and Glu adsorption. The PXRD analysis showed that the diffractograms obtained before and after the adsorption of amino acids have a similar pattern. The FT-IR spectra of the adsorbed material presented specific bands, which are related to the amino acids. The concentration range varied up to the anion solubility product and the extraction rate lay between 2.7 and 23.4% at higher equilibrium concentrations, showing that Mg-Al-CO₃-LDH is efficient at removing the amino acids from the aqueous medium.     

Temperature and concentration dependence of SANS spectra of aqueous solutions of short-chain amphiphiles

The small-angle neutron scattering (SANS) of some aqueous solutions of short-chain amphiphiles (glycols, diglycols, diols) has been measured as a function of concentration and temperature. The analysis of the spectra in terms of the Teubner-Strey phenomelogical formula indicates that, on increasing the concentration of the amphiphile, the structure of all these systems evolves in a similar way, i.e. a transition from disordered structures toward correlated aggregates (microstructures). The transition is depressed by increasing the temperature.     

Utilization of Mg2Al–layered double hydroxide as an effective sequestrator to trap Cu(II) ions from aqueous solution impacted by water quality parameters

Recently, Mg₂Al–layered double hydroxide (Mg₂Al–LDH) has been extensively studied as promising candidates to trap metal ions due to their high complexation and adsorption capacity. Herein, Mg₂Al–LDH was utilized as an effectiveness sequestrator to trap Cu(II) ions from aqueous solution by an adsorption process using batch technique under ambient conditions. The results showed that Cu(II) adsorption on Mg₂Al–LDH increases with pH increasing and maintains a high level at pH>7.0. The adsorption of Cu(II) was obviously affected by ionic strength at low pH, which was not dependent on ionic strength at high pH. The presence of HA or FA promotes the adsorption of Cu(II) on Mg₂Al–LDH at low pH values, while reduces the adsorption of Cu(II) at high pH values. The adsorption isotherms of Cu(II) on Mg₂Al–LDH at three different temperatures were simulated by the Langmuir, Freundlich, and Dubinin-Radushkevitch (D–R) models very well. The thermodynamic parameters were determined from the temperature-dependent adsorption, and the results showed that Cu(II) adsorption on Mg₂Al–LDH was exothermic and the process was favored at high temperature. The results suggest that Mg₂Al–LDH is suitable as a sorbent material for the recovery and attenuation of Cu(II)-polluted wastewater.     

A small angle neutron scattering study on the mixtures of pluronic L121 and anionic surfactant AOT

Small angle neutron scattering (SANS) experiments have been carried out on the micellar solutions containing mixtures of a hydrophobic triblock copolymer (L121, EO₅PO₆₈EO₅) and a hydrophobic anionic surfactant (AOT, sodium bis(2-ethylhexyl)sulphosuccinate) in water with varying ratio (R) of AOT to L121 for R = 0.15, 0.2, 0.3, 0.5 and 0.6. It is known that either L121 or AOT alone forms vesicles in water, but in the mixture with appropriate ratio of the two components a thermodynamically stable, isotropic solution of apparently small micelle-like aggregates is formed. We find that these micelles are prolate ellipsoidal.      

Reverse microemulsion-directed synthesis of hydroxyapatite nanoparticles under hydrothermal conditions

Morphology controllable hydroxyapatite (HA) nanoparticles were synthesized using reverse microemulsion (aqueous solution/TX-100/n-butanol/cyclohexane) systems under hydrothermal conditions. The concentration of cetyltrimethylammonium bromide (CTAB) contained in the aqueous solution and pH value had significant effect on the morphology and crystal phases of the final products. All the as-synthesized HA nanoparticles had a larger a value but smaller c value compared with the standard values of the JCPDs card. The existence of CTAB could be attributed to the growth of HA along an axis, but inhibit the growth along the c-axis to some extent. A proposed model was established to explain the change of the lattice parameters.     

二元合金微观偏析的相场法数值模拟

使用耦合溶质场的相场模拟研究了Ni-Cu二元合金枝晶生长过程中固相溶质扩散系数D_s 对枝晶形貌和微观偏析等的影响.计算结果表明，随着D_s的减少，固液界 面前沿溶质扩散层越薄，枝晶生长越有利，枝晶尖端生长的速度越大，侧向分支越发达；D< sub>s越小，固相中溶质成分的波动越强烈，随着D_s的增大，固相中溶质 成分的波动相应减小；溶质微观偏析程度随D_s的增大而减小. 关键词： 相场方法 微观偏析 固相扩散系数 数值模拟     

Transition from rigid to flexible structures in micelles of Undecylammonium chloride in aqueous solutions of NaCl

Small angle neutron scattering (SANS) data for Undecylammonium chloride (UAC) in heavy water in the presence of NaCl 0.0428 and 0.3422 M are consistent with the presence of elongated micelles. This micellar shape has been adopted to analyze viscosity data of UAC in water in the presence of NaCl. The results obtained from this last technique are consistent with the increase of the micelle aggregation number with increasing the surfactant concentration. Micelles change from prolate ellipsoidal shape to cylindrical and wormlike shapes by increasing the added NaCl concentration and surfactant concentrations. The differences between results for the micelle aggregation number calculated from viscosity, SANS and light scattering data have been attributed to the solvent effect on micelle formation as well as changes in the size, shape and flexibility of the micelle. Viscosity data provide qualitative information on the effect of the added NaCl concentration and surfactant concentration on the size, shape, flexibility of the micelles in diluted solutions.     

Degradation of C.I. Direct Black 168 from aqueous solution by fly ash/H2O2 combining ultrasound

Degradation of C.I. Direct Black 168 from aqueous solution using Fenton-like reactions combining ultrasound was investigated. In the presence of H₂O₂, the effect of the heterogeneous catalysts, such as fly ash, kaolinite or diatomaceous earth on the degradation of Direct Black 168 was observed under ultrasound. The fly ash was the most efficient catalyst. It is apparent that ultrasound can prompt the reaction to take place and give in higher degradation. In the combination of ultrasound and fly ash/H₂O₂, the effect of different system variables namely concentration of the dye, dosage of fly ash, concentration of H₂O₂, pH of solution and the addition of NaCl were studied. 99.0% removal ratio was achieved at initial concentration 100 mg/L, pH 3.0, and dosage of fly ash 2.0 g/L, as well as 2.94 mM H₂O₂. NaCl exhibited only a minor effect on the dye removal.     

Numerical simulations of sonochemical production and oriented aggregation of BaTiO3 nanocrystals

Numerical simulations of sonochemical production and oriented attachment of BaTiO₃ nanocrystals are performed in aqueous solution with pH 14. It is suggested that most significant effect of ultrasound is the dissolution of Ti-based gel in aqueous solution. It results in the dissolution-precipitation mechanism in the production of BaTiO₃ nanoparticles, while with mechanical stirring without ultrasound it is the in situ mechanism that BaTiO₃ is gradually formed on Ti-based gel. The oriented attachment of spherical BaTiO₃ nanocrystals occurs by van der Waals torque (Casimir torque). Large aggregates of nanocrystals do not attach with each other as the repulsive double layer interaction is stronger for larger aggregates. For smaller spherical nanocrystals, the alignment of the crystal axes is less accurate due to more significant rotational Brownian motion of the nanocrystals.     

Theory of XMCD spectra at the L2,3 absorption edges of mixed valence Ce and Yb compounds in high magnetic fields

We examine the structure of aggregates formed due to DNA interaction with dipalmitoylphosphatidylcholine (DPPC) in presence of Ca²⁺ and Zn²⁺ using small-angle synchrotron X-ray diffraction (SAXD) and neutron scattering (SANS). SAXD shows structural heterogeneity as a function of the cation concentration and temperature: At low cation concentration (∼1 mM), aggregates show two DPPC phases, one with a lateral segregation of DNA and cation, while higher cation concentration improves the DNA packing and the condensed lamellar phase is observed in DNA+DPPC+20mMion²⁺ aggregates. The SANS detected the dissolution of the condensed lamellar phase into unilamellar DPPC+Zn²⁺ vesicles due to gel ↦ liquid-crystal phase transition in DNA+DPPC+20mM Zn²⁺ aggregates with the short fragmented salmon sperm DNA.     

Diffusionless crystal growth in a eutectic system during rapid solidification

Experiments on nonequilibrium rapid eutectic growth are surveyed. The applicability limits of the modern theoretical models describing rapid solidification of binary systems are assessed. A problem of rapid eutectic growth when the local equilibrium is violated in the solute diffusion field (in the bulk liquid and at the solid-liquid interface) is formulated. An analytical solution to the problem of rapid lamellar eutectic growth under local nonequilibrium conditions in the solute diffusion field is found. It is shown that the diffusion-limited growth of a eutectic pattern ceases as soon as a chemically homogeneous crystalline phase begins to grow when the critical point V=V _D is achieved (V is the solid-liquid interface velocity and V _D is the solute diffusion speed in the bulk liquid). At V ≥ V _D, eutectic decomposition is suppressed and the nascent homogeneous crystalline phase has the initial (nominal) chemical composition of the binary system.     

Sphere-to-rod transition of triblock copolymer micelles at room temperature

A room temperature sphere-to-rod transition of the polyethylene oxide-polypropylene oxide-polyethylene oxide-based triblock copolymer, (PEO)₂₀(PPO)₇₀ (PEO)₂₀ micelles have been observed in aqueous medium under the influence of ethanol and sodium chloride. Addition of 5–10% ethanol induces a high temperature sphere-to-rod transition of the micelles, which is brought to room temperature upon addition of NaCl. The inference about the change in the shape of the micelles has been drawn from small-angle neutron scattering (SANS) and viscosity studies.