Effects of self energy of the ions on the double layer structure and properties at the dielectric interface

Although numerous theoretical efforts have been put forth, a systematic, unified and predictive theoretical framework that is able to capture all the essential physics of the interfacial behaviors of ions, such as the Hofmeister series effect, Jones-Ray effect and the salt effect on the bubble coalescence remain an outstanding challenge. The most common approach to treating electrostatic interactions in the presence of salt ions is the Poisson-Boltzmann (PB) theory. However, there are many systems for which the PB theory fails to offer even a qualitative explanation of the behavior, especially for ions distributed in the vicinity of an interface with dielectric contrast between the two media (like the water-vapor/oil interface). A key factor missing in the PB theory is the self energy of the ion.

In this thesis, we develop a self-consistent theory that treats the electrostatic self energy (including both the short-range Born solvation energy and the long-range image charge interactions), the nonelectrostatic contribution of the self energy, the ion-ion correlation and the screening effect systematically in a single framework. By assuming a finite charge spread of the ion instead of using the point-charge model, the self energy obtained by our theory is free of the divergence problems and gives a continuous self energy across the interface. This continuous feature allows ions on the water side and the vapor/oil side of the interface to be treated in a unified framework. The theory involves a minimum set of parameters of the ion, such as the valency, radius, polarizability of the ions, and the dielectric constants of the medium, that are both intrinsic and readily available. The general theory is first applied to study the thermodynamic property of the bulk electrolyte solution, which shows good agreement with the experiment result for predicting the activity coefficient and osmotic coefficient.

Next, we address the effect of local Born solvation energy on the bulk thermodynamics and interfacial properties of electrolyte solution mixtures. We show that difference in the solvation energy between the cations and anions naturally gives rise to local charge separation near the interface, and a finite Galvani potential between two coexisting solutions. The miscibility of the mixture can either increases or decreases depending on the competition between the solvation energy and translation entropy of the ions. The interfacial tension shows a non-monotonic dependence on the salt concentration: it increases linearly with the salt concentration at higher concentrations, and decreases approximately as the square root of the salt concentration for dilute solutions, which is in agreement with the Jones-Ray effect observed in experiment.

Next, we investigate the image effects on the double layer structure and interfacial properties near a single charged plate. We show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. The image charge effect is then studied for electrolyte solutions between two plates. For two neutral plates, we show that depletion of the salt ions by the image charge repulsion results in short-range attractive and long-range repulsive forces. If cations and anions are of different valency, the asymmetric depletion leads to the formation of an induced electrical double layer. For two charged plates, the competition between the surface charge and the image charge effect can give rise to like- charge attraction.

Then, we study the inhomogeneous screening effect near the dielectric interface due to the anisotropic and nonuniform ion distribution. We show that the double layer structure and interfacial properties is drastically affected by the inhomogeneous screening if the bulk Debye screening length is comparable or smaller than the Bjerrum length. The width of the depletion layer is characterized by the Bjerrum length, independent of the salt concentration. We predict that the negative adsorption of ions at the interface increases linearly with the salt concentration, which cannot be captured by either the bulk screening approximation or the WKB approximation. For asymmetric salt, the inhomogeneous screening enhances the charge separation in the induced double layer and significantly increases the value of the surface potential.

Finally, to account for the ion specificity, we study the self energy of a single ion across the dielectric interface. The ion is considered to be polarizable: its charge distribution can be self-adjusted to the local dielectric environment to minimize the self energy. Using intrinsic parameters of the ions, such as the valency, radius, and polarizability, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

The theory developed in this work represents the most systematic theoretical technique for weak-coupling electrolytes. We expect the theory to be more useful for studying a wide range of structural and dynamic properties in physicochemical, colloidal, soft-matter and biophysical systems.

Theory of the positive column of a gas discharge

An attempt is made to provide a theoretical explanation of the effect of the positive column on the voltage-current characteristic of a glow or an arc discharge. Such theories have been developed before, and all are based on balancing the production and loss of charged particles and accounting for the energy supplied to the plasma by the applied electric field. Differences among the theories arise from the approximations and omissions made in selecting processes that affect the particle and energy balances. This work is primarily concerned with the deviation from the ambipolar description of the positive column caused by space charge, electron-ion volume recombination, and temperature inhomogeneities.

The presentation is divided into three parts, the first of which involved the derivation of the final macroscopic equations from kinetic theory. The final equations are obtained by taking the first three moments of the Boltzmann equation for each of the three species in the plasma. Although the method used and the equations obtained are not novel, the derivation is carried out in detail in order to appraise the validity of numerous approximations and to justify the use of data from other sources. The equations are applied to a molecular hydrogen discharge contained between parallel walls. The applied electric field is parallel to the walls, and the dependent variables—electron and ion flux to the walls, electron and ion densities, transverse electric field, and gas temperature—vary only in the direction perpendicular to the walls. The mathematical description is given by a sixth-order nonlinear two-point boundary value problem which contains the applied field as a parameter. The amount of neutral gas and its temperature at the walls are held fixed, and the relation between the applied field and the electron density at the center of the discharge is obtained in the process of solving the problem. This relation corresponds to that between current and voltage and is used to interpret the effect of space charge, recombination, and temperature inhomogeneities on the voltage-current characteristic of the discharge.

The complete solution of the equations is impractical both numerically and analytically, and in Part II the gas temperature is assumed uniform so as to focus on the combined effects of space charge and recombination. The terms representing these effects are treated as perturbations to equations that would otherwise describe the ambipolar situation. However, the term representing space charge is not negligible in a thin boundary layer or sheath near the walls, and consequently the perturbation problem is singular. Separate solutions must be obtained in the sheath and in the main region of the discharge, and the relation between the electron density and the applied field is not determined until these solutions are matched.

In Part III the electron and ion densities are assumed equal, and the complicated space-charge calculation is thereby replaced by the ambipolar description. Recombination and temperature inhomogeneities are both important at high values of the electron density. However, the formulation of the problem permits a comparison of the relative effects, and temperature inhomogeneities are shown to be important at lower values of the electron density than recombination. The equations are solved by a direct numerical integration and by treating the term representing temperature inhomogeneities as a perturbation.

The conclusions reached in the study are primarily concerned with the association of the relation between electron density and axial field with the voltage-current characteristic. It is known that the effect of space charge can account for the subnormal glow discharge and that the normal glow corresponds to a close approach to an ambipolar situation. The effect of temperature inhomogeneities helps explain the decreasing characteristic of the arc, and the effect of recombination is not expected to appear except at very high electron densities.

The kingdom of the shore: achievement of good ecological potential in reservoirs

The European Water Framework Directive requires member states to restore aquatic habitats to good ecological status (quality) by 2015. Good ecological status is defined as slightly different from high status, which, according to the Directive, means negligible human influence. This poses problems enough for restoration of natural habitats but artificial reservoirs are not excluded from the Directive. They must be restored to good ecological potential. The meaning of good ecological status is linked to that of 'high' ecological status, the pristine reference condition for aquatic habitats under the Directive. From the point of view of an ecologist, this is taken to mean the presence of four fundamental characteristics: nutrient parsimony, characteristic biological and physical structure, connectivity within a wider system and adequate size to give resilience of the biological communities to environmental change. These characteristics are strongly interrelated. Ecological potential must bear some relationship to ecological status but since the reference state for ecological quality is near absence of human impact, it is difficult to see how the criteria for ecological status can be applied to a completely man-made entity where the purpose of the dam is deliberately to interfere with the natural characteristics of a river or former natural lake. Rservoirs are disabled lakes, ususally lakcing the diversity and function provided by a littoral zone. Nonetheless, pragmatic approaches to increasing the biodiversity of reservours are reviewed and conclusions drawn as to the likely effectivemess of the legislation.

Spring-to-Spring Balancing as Energy-Free Adjustment Method in Gravity Equilibrators

Generally, adjustment of gravity equilibrator to a new payload requires energy, e.g. to increase the pre-load of the balancing spring. A novel way of energy-free adjustment of gravity equilibrators is possible by introducing the concept of a storage spring. The storage spring supplies or stores the energy necessary to adjust the balancer spring of the gravity equilibrator. In essence the storage spring mechanism maintains a constant potential energy within the spring mechanism; energy is exchanged between the storage and balancer spring when needed. Various conceptual designs using both zero-free-length springs and regular extension springs are proposed. Two models were manufactured demonstrating the practical embodiments and functionality.

Quantum measurement of an electron in a disordered potential: Delocalization versus measurement voltages

Quantum point contact (QPC), one of the typical mesoscopic transport devices, has been suggested to be an efficient detector for quantum measurement. In the context of two-state charge qubit, our previous studies showed that the QPC's measurement back-action cannot be described by the conventional Lindblad quantum master equation. In this work, we study the measurement problem of a multistate system, say, an electron in disordered potential, subject to the quantum measurement of the mesoscopic detector QPC. The effect of measurement back-action and the detector's readout current are analyzed, where particular attention is focused on some new features and the underlying physics associated with the measurement-induced delocalization versus the measurement voltages.

Gate controlled Aharonov-Bohm-type oscillations from single neutral excitons in quantum rings

We report on a magnetophotoluminescence study of single self-assembled semiconductor nanorings which are fabricated by molecular-beam epitaxy combined with AsBr3 in situ etching. Oscillations in the neutral exciton radiative recombination energy and in the emission intensity are observed under an applied magnetic field. Further, we control the period of the oscillations with a gate potential that modifies the exciton confinement. We infer from the experimental results, combined with calculations, that the exciton Aharonov-Bohm effect may account for the observed effects.

Decomposition of Noncommutative U(1) Gauge Potential

We investigate the decomposition of noncommutative gauge potential (A) over cap (i), and find that it has inner structure, namely, (A) over cap (i) can he decomposed in two parts, (b) over cap (i) and (a) over cap (i), where (b) over cap (i) satisfies gauge transformations while (a) over cap (i) satisfies adjoint transformations, so close the Seiberg-Witten mapping of noncommutative, U(1) gauge potential. By, means of Seiberg-Witten mapping, we construct a mapping of unit vector field between noncommutative space and ordinary space, and find the noncommutative U(1) gauge potential and its gauge field tensor can be expressed in terms of the unit vector field. When the unit vector field has no singularity point, noncommutative gauge potential and gauge field tensor will equal ordinary gauge potential and gauge field tensor

Separation of drug enantiomers by capillary electrophoresis in the presence of neutral cyclodextrins

This is a selected review, highlighting our results obtained in an extended screening program ("The German-Chinese Drug Screening Program"), with a focus on a set of original data obtained with heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin(TM-beta-CD) as the chiral solvating agent (CSA). The enantioseparation of 86 drugs by capillary zone electrophoresis in the presence of this CSA was successful for 47 drugs. The migration separation factors (alpha(m)) and the migration retardation factors (R-m) were compared with those found for native beta-cyclodextrin (beta-CD). The patterns thus obtained were also compared with those observed for hexakis(2,3,6-tri-O-methyl)-alpha-CD (TM-alpha-CD) and octakis(2,3,6-tri-O-methyl)-gamma-CD (TM-gamma-CD), respectively. From the statistical data, it can be concluded that there is a remarkable influence of the analyte structure on the electrophoretic data. A substructure 4H was found in the analyte structure that has a significant influence on the analytes' behaviour. Thus, analytes bearing the substructure 4H do not only have a strong affinity to the CDs but also a high rate of success of chiral separation in all systems reviewed. In light of this, the different ring sizes of native cyclodextrins (alpha-, beta- and gamma-CD) readily explain their behaviour towards a limited test set of chiral drugs. Sterical considerations point to the significance of side-on-binding versus inclusion in the cavity of the host. In addition to the findings from the screening program, numerous references to the Literature are given. (C) 2000 Elsevier Science B.V. All rights reserved.

Comparison between Gd-DTPA and several bisamide derivatives as potential MRI contrast agents

Four neutral gadolinium complexes of diethylenetriaminepentaacetic acid (DTPA)-bisamide derivatives have been synthesized and characterized. Their potential application as tissue-specific and low-osmolarity MRI contrast agents has been evaluated by in vitro and in vivo experiments. Their measured relaxivities in D2O, bovine serum albumin and human serum transferrin solutions showed favorable relaxation ability. In vivo studies have proven that Gd(DTPA-BDMA), Gd(DTPA-BIN), and Gd(cyclic-DTPA-1,2-pn) could be promising liver-specific MRI contrast agents and Gd(DTPA-BDMA), and Gd(cyclic-DTPA-1,2-pn) have favorable renal excretion capability. Among them, Gd(cyclic-DTPA-1,2-pn) is a more powerful hepatic contrast agent and Gd(DTPA-BIN) provides the stable imaging contrast for several hours. They also show a lower toxicity.

REDOX THERMODYNAMICS OF CYTOCHROME-C AT THE BARE GLASSY-CARBON ELECTRODE

Investigation of the redox thermodynamics of horse heart cytochrome c at bare glassy carbon electrodes has been performed using cyclic voltammetry with a nonisothermal electrochemical cell. The thermodynamic parameters of the electron-transfer reaction of cytochrome c have been estimated in different component buffer solutions. The change DELTAS(re)-degrees in reaction center entropy and the formal potential E-degrees' (at 25-degrees-C, vs. standard hydrogen electrode (SHE)) for cytochrome c are found to be -64.1 J K-1 mol-1 and 0.251 V in phosphate buffer, -64.8 J K-1 mol-1 and 0.257 V in Tris + HCl buffer, -65.6 J K-1 mol-1 and 0.261 V in Tris+CH3COOH buffer (pH 7.0, ionic strength 100 mM). The temperature dependence of the formal potential obtained in phosphate buffer with or without NaCl in the range 5-55-degrees-C shows biphase characteristics in an alkaline solution with an intersection point at ca. 44-degrees-C or 42-degrees-C, which should be due to a structural change in the protein moiety of cytochrome c. However, in acidic and neutral solutions only a monotonic relationship between E-degrees' and temperature is observed. The effect of the buffer component on E-degrees' for cytochrome c is also discussed.

Seeding nets with neutral spores of the red alga Porphyra umbilicalis (L.) Kutzing for use in integrated multi-trophic aquaculture (IMTA)

Nets in traditional Porphyra mariculture are seeded with conchospores derived from the conchocelis phase, and spend a nursery period in culture tanks or calm coastal waters until they reach several centimeters in length. Some species of Porphyra can regenerate the foliose phase directly through asexual reproduction, which suggests that the time, infrastructure, and costs associated with conchocelis culture might be avoided by seeding nets with asexual spores. Here, we present work from a short-term mariculture study using nets seeded with asexual spores (neutral spores) of a native Maine species of Porphyra. Porphyra umbilicalis (L.) Kutzing was selected for this proof of concept research because of its reproductive biology, abundance across seasons in Maine, and evidence of its promise as a mariculture crop. We studied the maturation, release, and germination of the neutral spores to develop an appropriate seeding protocol for nets, followed by development of a nursery raceway to provide an easily manipulated environment for the seeded nets. Neutral spores were produced throughout the year on the central Maine coast,however, there was a temporal variability in the number and survival of released neutral spores, depending upon thallus position in the intertidal zone. Small thalli were strictly vegetative, but most thalli reproduced by neutral spores- sexual reproduction was absent. Neutral spores germinated quickly at 10 and 15 'C, but germination was delayed at 5 degrees C. Unlike some algal zygotes and spores, neutral spores of R umbilicalis required light to germinate; however, irradiances of 25 and 100 mu mol photons M-2 S-1 were equally sufficient for germination. Rafts of seeded nets were deployed in Cobscook Bay, Maine, at two distances from salmon aquaculture pens and at a control site on a nearby, fallow aquaculture site (no salmon). There was no difference in nitrogen content of harvested thalli; however, both the density and the surface area of harvested thalli were different among the sites. The possible causes of these differences are discussed in the context of potential use of P umbilicalis in IMTA. (C) 2007 Elsevier B.V. All rights reserved.

Equatorial pacific SSTA-related decadal variations of potential predictability of ENSO and interannual climate

Based on analysis of NCEP reanalysis data and SST indices of the recent 50 years, decadal changes of the potential predictability of ENSO and interannual climate anomalies were investigated. Autocorrelation of Nino3 SST anomalies (SSTA) and correlation between atmospheric anomalies fields and Nino3 SSTA exhibit obvious variation in different decades, which indicates that Nino3 SSTA-related potential predictability of ENSO and interannual climate anomalies has significant decadal changes. Time around 1977 is not only a shift point of climate on the interdecadal time scale but also a catastrophe point of potential predictability of ENSO and interannual climate. As a whole, ENSO and the PNA pattern in boreal winter are more predictable in 1980s than in 1960s and 1970s, while the Nino3 SSTA-related potential predictability of the Indian monsoon and the East Asian Monsoon is lower in 1980s than in 1960s and 1970s.

Millstone Hill电离层F层等效风场的气候学研究

Neutral winds and electric fields in the ionospheric F layer play important roles in the variations of the ionosphere, and also affect the thermospheric circulation via the close coupling between the ionosphere and the thermosphere. By now, the neutral winds and electric drifts are generally observed with ground-based Fabry-Perot interferometers (FPI) and incoherent scatter radars (ISR), rockets, and satellite-borne instrument. Based on the servo theory, the ionospheric equivalent winds, which include the information of both the neutral winds and electric fields, can be derived from these characteristic parameters observed by ionosondes. This indirect derivation has potential values in climatological researches and space weather forecast. With the data set of the incoherent scatter radar observations at Millstone Hill, USA, from 1976 to 2006, we statistically analyzed the climatological variations of the vertical component of the equivalent winds (VEWs) over Millstone Hill, which are derived from the ionospheric key parameters (the peak electron number density and peak height of the F2 layer, NmF2 and hmF2) on the basis of the servo theory, Liu's method, and measurements from the ion line-of-sight velocity as well. The main results of this analysis are summarized as follows: (1) The values of VEWs over Millstone Hill during nighttime are stronger than in the daytime, and the upward drift dominates most of the day. In 1993, Hagan found that the component of the neutral winds in the magnetic meridion in daytime is weaker than during nighttime under both solar maximum and minimum conditions; he also found that the equatorward winds dominate most of the day. Both results suggest that the thermosphere in Millstone Hill is modulated by the aurorally driven high-latitude circulation cell; that is, during geomagnetic quiet periods, the average auroral activity is strong enough to drive thermospheric circulation equatorward for most of the day at Millstone Hill. Moreover, since ion drag is the strongest during daytime when F region densities are enhanced by photoionization, the wind speeds are smaller during the daytime than in the nighttime. (2) There is equinoctial symmetry in VEWs at Millstone Hill. The amplitudes and phases of VEWs in spring are quite similar to those in autumn. In contrast, the nighttime upward drift in winter is weaker than in summer and the difference becomes more significant with increasing solar activity. This solstice asymmetry indicates that, the aurorally driven circulation in the northern hemisphere at Millstone Hill latitude is weaker in winter due to arctic darkness, because the subsolar point is in the southern hemisphere. (3) The comparison of the VEWs derived from three methods, i.e., the servo theory, Liu's method, and the ISR ion line-of-sight velocity measurements, indicates that the amplitudes and main phase tendencies of these VEWs accord well with each other during nighttime hours. However, the case in the daytime is relatively worse. This daytime discrepancy can be explained in terms of the effects of photochemical processes and the choices of the servo constants. A larger servo constant gives a stronger plasma drift in daytime. Therefore, this study tells how important to choose a suitable constant for deriving VEWs at Millstone Hill.

Automatic point correspondence and registration based on linear structures

R. Marti, R. Zwiggelaar, C.M.E. Rubin, 'Automatic point correspondence and registration based on linear structures', International Journal of Pattern Recognition and Artificial Intelligence 16 (3), 331-340 (2002)