X-ray study of the electric double layer at the n-hexane/nanocolloidal silica interface

The spatial structure of the transition region between an insulator and an electrolyte solution was studied with x-ray scattering.The electron density profile across the n-hexane/silica sol interface (solutions with 5-nm, 7-nm, and 12-nm colloidal particles) agrees with the theory of the electrical double layer and shows separation of positive and negative charges. The interface consists of three layers, i.e., a compact layer of Na+, a loose monolayer of nanocolloidal particles as part of a thick diffuse layer, and a low-density layer sandwiched between them. Its structure is described by a model in which the potential gradient at the interface reflects the difference in the potentials of "image forces" between the cationic Na+ and anionic nanoparticles and the specific adsorption of surface charge. The density of water in the large electric field (1-10 GV/m) of the transition region and the layering of silica in the diffuse layer is discussed.Comment: 9 pages, 9 figure

The Kinetics of the Adiabatic and Nonadiabatic Reactions at the Metal and Semiconductor Electrodes

The basic results of the correct quantum-mechanical calculqtions of the probability of the elementary act of adiabatic homogeneous reactions are summarized. The calculations are carried out for the model of the one-dimensional potential energy curves without using the perturbation theory. The adiabatic and nonadiabatic electrochemical reactions at the metal and semiconductor electrodes are considered. The physical picture of the process is discussed. The adiabatic electrochemical process is shown to be of the many-electron character. The expressions for the transition probability is derived for the metal and semiconductor electrodes. The redox reactions at the semiconductor are considered in the presence of the surface states

The Kinetics of the Adiabatic and Nonadiabatic Reactions at the Metal and Semiconductor Electrodes

The basic results of the correct quantum-mechanical calculqtions of the probability of the elementary act of adiabatic homogeneous reactions are summarized. The calculations are carried out for the model of the one-dimensional potential energy curves without using the perturbation theory. The adiabatic and nonadiabatic electrochemical reactions at the metal and semiconductor electrodes are considered. The physical picture of the process is discussed. The adiabatic electrochemical process is shown to be of the many-electron character. The expressions for the transition probability is derived for the metal and semiconductor electrodes. The redox reactions at the semiconductor are considered in the presence of the surface states

Crystals of Na+ ions at the surface of a silica hydrosol

I used x-ray grazing incidence diffraction to measure the spatial correlations between sodium ions adsorbed with Bjerrum's density at the surface of a monodispersed 22-nm-particle colloidal silica solution stabilized by NaOH with a total bulk concentration mol/L. My findings show that the surface compact layer is in a two-dimensional crystalline state (symmetry p2), with four ions forming the unit cell and a ~30 Angstrom translational correlation length between sodium ions.Comment: 13 pages, 4 figure

Ion-Size Effect at the Surface of a Silica Hydrosol

The author used synchrotron x-ray reflectivity to study the ion-size effect for alkali ions (Na$^+$, K$^+$, Rb$^+$, and Cs$^+$), with densities as high as $4 \times 10^{18}- 7 \times 10^{18}$ m$^{-2}$, suspended above the surface of a colloidal solution of silica nanoparticles in the field generated by the surface electric-double layer. According to the data, large alkali ions preferentially accumulate at the sol's surface replacing smaller ions, a finding that qualitatively agrees with the dependence of the Kharkats-Ulstrup single-ion electrostatic free energy on the ion's radius.Comment: 17 pages, 4 figure

Torsional fluctuations in columnar DNA assemblies

In columnar assemblies of helical bio-molecules the azimuthal degrees of freedom, i.e. rotations about the long axes of molecules, may be important in determining the structure of the assemblies especially when the interaction energy between neighbouring molecules explicitly depends on their relative azimuthal orientations. For DNA this leads to a rich variety of mesophases for columnar assemblies, each categorized by a specific azimuthal ordering. In a preceding paper [A. Wynveen, D. J. Lee, and A. A. Kornyshev, Eur. Phys. J. E, 16, 303 (2005)] a statistical mechanical theory was developed for the assemblies of torsionally rigid molecues in order to determine how thermal fluctuations influence the structure of these mesophases. Here we extend this theory by including torsional fluctuations of the molecules, where a DNA molecule may twist about its long axis at the cost of torsional elastic energy. Comparing this with the previous study, we find that inclusion of torsional fluctuations further increases the density at which the transition between the hexagonal structure and the predicted rhombic phase occurs and reduces the level of distortion in the rhombic phase. As X-ray diffraction may probe the 2-D lattice structure of such assemblies and provide information concerning the underlying interaction between molecules, we have also calculated correlation functions for the azimuthal ordering which are manifest in an x-ray scattering intensity profiles.Comment: 33 pages, 8 figure

Ionic liquids at electrified interfaces

Until recently, “room-temperature” (<100–150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)–(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of “first-generation” room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the “later generation” RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in “cocktails” of one’s choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost “universal” solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) “sister-systems”.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules

Epidemiology, practice of ventilation and outcome for patients at increased risk of postoperative pulmonary complications

BACKGROUND Limited information exists about the epidemiology and outcome of surgical patients at increased risk of postoperative pulmonary complications (PPCs), and how intraoperative ventilation was managed in these patients. OBJECTIVES To determine the incidence of surgical patients at increased risk of PPCs, and to compare the intraoperative ventilation management and postoperative outcomes with patients at low risk of PPCs. DESIGN This was a prospective international 1-week observational study using the ‘Assess Respiratory Risk in Surgical Patients in Catalonia risk score’ (ARISCAT score) for PPC for risk stratification. PATIENTS AND SETTING Adult patients requiring intraoperative ventilation during general anaesthesia for surgery in 146 hospitals across 29 countries. MAIN OUTCOME MEASURES The primary outcome was the incidence of patients at increased risk of PPCs based on the ARISCAT score. Secondary outcomes included intraoperative ventilatory management and clinical outcomes. RESULTS A total of 9864 patients fulfilled the inclusion criteria. The incidence of patients at increased risk was 28.4%. The most frequently chosen tidal volume (VT) size was 500 ml, or 7 to 9 ml kg1 predicted body weight, slightly lower in patients at increased risk of PPCs. Levels of positive end-expiratory pressure (PEEP) were slightly higher in patients at increased risk of PPCs, with 14.3% receiving more than 5 cmH2O PEEP compared with 7.6% in patients at low risk of PPCs (P < 0.001). Patients with a predicted preoperative increased risk of PPCs developed PPCs more frequently: 19 versus 7%, relative risk (RR) 3.16 (95% confidence interval 2.76 to 3.61), P < 0.001) and had longer hospital stays. The only ventilatory factor associated with the occurrence of PPCs was the peak pressure. CONCLUSION The incidence of patients with a predicted increased risk of PPCs is high. A large proportion of patients receive high VT and low PEEP levels. PPCs occur frequently in patients at increased risk, with worse clinical outcome