Influence of NaCl on the behavior of PEO-PPO-PEO triblock copolymers in solution, at interfaces, and in asymmetric liquid films

The solution behavior of the polymeric surfactant Pluronic F127 (PEO(99)PPO(65)PEO(99)) and its adsorption behavior on aqueous-silica and aqueous-air interfaces, as well as the disjoining pressure isotherms of asymmetric films (silica/aqueous film/air) containing F127, are studied. The interfacial properties of adsorbed F127 layers (the adsorbed amount Gamma and the thickness h) as well as the aqueous wetting film properties [film thickness (h) and refractive indexes] were studied via ellipsometry. The solution properties of F127 were investigated using surface tensiometry and light scattering. The interactions between the air-water and silica-water interfaces were measured with a thin film pressure balance technique (TFB) and interpreted in terms of disjoining pressure as a function of the film thickness. The relations between the behaviors of the asymmetric films, adsorption at aqueous air, and aqueous silica interfaces and the solution behavior of the polymeric surfactant are discussed. Special attention is paid to the influence of the concentrations of F127 and NaCl. Addition of electrolyte lowers the critical micelle concentration, diminishes adsorption on silica, and increases the thickness of the asymmetric film.     

Phosphorescence of thermally oxidised poly(butadiene) and model enones: temperature dependence

The temperature dependence of phosphorescence of model enone compounds in poly (methyl methacrylate) matrix and glassy methylcyclohexane/isopentane solution and of enones formed from thermal oxidation of poly (butadiene) has been studied over the temperature range 77–220°K. The single discontinuity in the plot for the model enone-glassy solvent is due to the freezing of a (solvent perturbed) barrier to rotation in the enone, and an analogous transition is also observed in the model enone poly (methyl methacrylate) samples and in thermally oxidised poly (butadiene). In the polymer matrices, a second transition corresponding to the γ-transition in poly (methyl methacrylate) and the glass transition temperature T_g in poly (butadiene) are also revealed in the Arrhenius plots. The results demonstrate that care must be taken in ascribing such discontinuities solely to polymer properties since intrinsic properties of the luminescence probe itself may exhibit similar features.     

Adsorption geometry of 4-picoline chemisorbed on the Cu(110) surface: a study of forces controlling molecular self-assembly

The adsorption of 4-picoline (4-methylpyridine) on the Cu(110) surface has been studied with time-of-flight electron stimulated desorption ion angular distribution (TOF-ESDIAD) and other methods. Using deuterium labeling in the methyl group and hydrogen labeling on the aromatic ring, it has been possible to separately monitor by TOF-ESDIAD the C-D bond directions and the C-H bond directions in the adsorbed molecule. These triangulation measurements have led to a detailed understanding of the conformation of the adsorbed molecule relative to the Cu(110) crystal lattice, allowing one to witness changes in the molecular conformation as adsorbate-adsorbate interactional effects take place for increasing coverages. At low coverages, the molecule adsorbs by the N atom at an atop Cu site with the aromatic ring parallel to the <001> azimuth and with the molecular axis inclined 33 (+/- 5) degrees along the <001> azimuth. As rows of 4-picoline molecules form long range ordered chain structures oriented along the <112> azimuth, the aromatic ring twists 29 degrees about the inclined molecular axis as a result of forces between the adsorbate molecules. The initial tilting of the molecular axis at low coverage is likely due to the interaction of the positive-outward dipole with its image in the substrate. The ring twist may result from dipoleminus signdipole forces between the adsorbate molecules in the rows formed tending to form nested parallel pyridine rings. These studies are the first to apply the TOF-ESDIAD method for the measurement of the direction of chemical bonds at more than one molecular location within an adsorbed molecule and the new method is named electron stimulated desorption-molecular triangulation (ESD-MT). The results obtained give information of importance in understanding the factors which control conformational effects during the molecular self-assembly of complex adsorbed molecules on surfaces.     

The microwave spectrum of thioformaldehyde,CD2S,and CH2S: Average structure,dipole moments,and 33S quadrupole coupling

Microwave transitions up to J = 53 in the ground vibrational state of deuterothioformaldehyde, CD₂S, were studied between 8 and 40 GHz. A detailed centrifugal distortion analysis yields accurate constants for comparison with force field values. The isotopic species ¹³CH₂S, CH₂³⁴S, CH₂³³S, ¹³CD₂S, CD₂³⁴S, and CD₂³³S were studied in natural abundance. Accurate average zero-point structures were determined for both CD₂S and CH₂S:

$\text{CH}{}_2\text{S}\text{CS}\text{=1.6138(4)}\text{CH}\text{= 1.0962(6)}\text{A}\text{?}\text{∠}\text{HCH}\text{=116° 16(6)′,}\text{CD}{}_2\text{S}\text{CS}\text{=1.6136(4)}\text{CD}\text{= 1.0931(4)}\text{A}\text{?}\text{∠}\text{DCD}\text{=116° 25(5)′}$

Changes in the zero-point geometry for deuterium substitution were established. Quadrupole fine structure arising from the ³³S nucleus has been measured in CH₂³³S and CD₂³³S. Analysis gives the following coupling constants (for both molecules) as χ_aa = ?11.7 and χ_bb - χ_cc = 88.1 MHz. The dipole moment of CD₂S was measured to be 1.6588(8)D and an accurate comparison with CH₂S was made; the ratio of dipole moments $\text{CD}{}_2\text{S}\text{CH}{}_2\text{S}$ was found to be 1.0062(4). The spectroscopic and bonding properties of CH₂S will be compared with formaldehyde and other molecules.     

The specific heat capacities of V2O5/P2O5-based glasses

The specific heat capacities of a series of V₂O₅/P₂O₅-based glasses have been measured in the approximate temperature range 3–300 K. The proportions of the host constituents were varied and the effects produced by adding oxides of copper, titanium and sodium were examined. The measurements were extended to investigate the influence of fast neutron irradiation upon the specific heat capacity of pure, initially crystalline V₂O₅.The observations are consistent with a spectrum of background vibrations, the form of which is temperature dependent. At intermediate temperatures the vibrations were consistent with the glasses displaying predominantly chain-like characteristics. With reduction to lower temperatures the vibrational behaviour increasingly resembled that of solids displaying three-dimensional characteristics. The temperature dependence of the specific heat capacity at the lowest temperatures was consistent with the presence of a narrow band of low-frequency modes centred upon 1.67 × 10¹¹ s^?1, the density of which increased with phosphorus content. From observations of the density of these modes in the doped specimens, it was concluded that the role of copper wass largely that of a network former, whereas titanium and sodium were essentially network modifiers.     

The input impedance of the dielectric resonator antenna

Dielectric cylinders of very high permittivity have been used in the past as resonant cavities, but since the structure is not enclosed by metallic walls, electromagnetic fields do exist beyond the geometrical boundaries of the structure and part of the power is radiated. Through the proper choice of geometry and permittivity this radiation can become the dominant feature of the structure and become an efficient antenna for use at millimeter wave frequencies. Both experimental and theoretical investigations of a variety of these dielectric resonator antennas have been undertaken. In particular, the input impedance of a probe-fed cylindrical structure was examined in detail and a comparison of theoretical and experimental results was made.     

Neural correlates of intelligibility in speech investigated with noise vocoded speech--a positron emission tomography study

Functional imaging studies of speech perception in the human brain have identified a key role for auditory association areas in the temporal lobes (bilateral superior temporal gyri and sulci) in the perceptual processing of the speech signal. This is extended to suggest some functional specialization within this bilateral system, with a particular role for the left anterior superior temporal sulcus (STS) in processing intelligible speech. In the current study, noise-vocoded speech was used to vary the intelligibility of speech parametrically. This replicated the finding of a selective response to intelligibility in speech in the left anterior superior temporal sulcus, in contrast to the posterior superior temporal sulcus, which showed a response profile insensitive to the degree of intelligibility. These results are related to theories of functional organization in the human auditory system, which have indicated that there are separate processing streams, with different functional roles, running anterior and posterior to primary auditory cortex. Specifically, it is suggested that an anterior stream processing intelligibility can be distinguished from a posterior stream associated with transient representations, important in spoken repetition and working memory.