151 research outputs found
Some Critical Remarks on the Paper Fixed Charge Double Layer Potential Equations - a Derivation by M. Mirnik
After a very lengthy correspondence in which I have repeatedly expressed
my criticism of the contents of Professor Mirnik\u27s Fixed charge double layer
potential equations, Profesor Mirnik has sent me a copy of the manuscript
as it has been accepted for publication and asked me to express my criticism in the same periodical
Some Critical Remarks on the Paper Fixed Charge Double Layer Potential Equations - a Derivation by M. Mirnik
After a very lengthy correspondence in which I have repeatedly expressed
my criticism of the contents of Professor Mirnik\u27s Fixed charge double layer
potential equations, Profesor Mirnik has sent me a copy of the manuscript
as it has been accepted for publication and asked me to express my criticism in the same periodical
Electrophoretic Properties of Highly Charged Colloids: A Hybrid MD/LB Simulation Study
Using computer simulations, the electrophoretic motion of a positively
charged colloid (macroion) in an electrolyte solution is studied in the
framework of the primitive model. Hydrodynamic interactions are fully taken
into account by applying a hybrid simulation scheme, where the charged ions
(i.e. macroion and electrolyte), propagated via molecular dynamics (MD), are
coupled to a Lattice Boltzmann (LB) fluid. In a recent experiment it was shown
that, for multivalent salt ions, the mobility initially increases with
charge density , reaches a maximum and then decreases with further
increase of . The aim of the present work is to elucidate the behaviour
of at high values of . Even for the case of monovalent microions,
we find a decrease of with . A dynamic Stern layer is defined
that includes all the counterions that move with the macroion while subject to
an external electrical field. The number of counterions in the Stern layer,
, is a crucial parameter for the behavior of at high values of
. In this case, the mobility depends primarily on the ratio
(with the valency of the macroion). The previous contention that
the increase in the distortion of the electric double layer (EDL) with
increasing leads to the lowering of does not hold for high
. In fact, we show that the deformation of the EDL decreases with
increase of . The role of hydrodynamic interactions is inferred from
direct comparisons to Langevin simulations where the coupling to the LB fluid
is switched off. Moreover, systems with divalent counterions are considered. In
this case, at high values of the phenomenon of charge inversion is
found.Comment: accepted in J. Chem Phys., 10 pages, 9 figure
Where the linearized Poisson-Boltzmann cell model fails: (I) spurious phase separation in charged colloidal suspensions
We perform a linearization of the Poisson-Boltzmann (PB) density functional
for spherical Wigner-Seitz cells that yields Debye-H\"uckel-like equations
agreeing asymptotically with the PB results in the weak-coupling
(high-temperature) limit. Both the canonical (fixed number of microions) as
well as the semi-grand-canonical (in contact with an infinite salt reservoir)
cases are considered and discussed in a unified linearized framework. In the
canonical case, for sufficiently large colloidal charges the linearized theory
predicts the occurrence of a thermodynamical instability with an associated
phase separation of the homogeneous suspension into dilute (gas) and dense
(liquid) phases. In the semi-grand-canonical case it is predicted that the
isothermal compressibility and the osmotic-pressure difference between the
colloidal suspension and the salt reservoir become negative in the
low-temperature, high-surface charge or infinite-dilution (of polyions) limits.
As already pointed out in the literature for the latter case, these features
are in disagreement with the exact nonlinear PB solution inside a Wigner-Seitz
cell and are thus artifacts of the linearization. By using explicitly
gauge-invariant forms of the electrostatic potential we show that these
artifacts, although thermodynamically consistent with quadratic expansions of
the nonlinear functional and osmotic pressure, may be traced back to the
non-fulfillment of the underlying assumptions of the linearization.Comment: 32 pages, 3 PostScript figures, submitted to J. Chem. Phy
Many-body interactions and melting of colloidal crystals
We study the melting behavior of charged colloidal crystals, using a
simulation technique that combines a continuous mean-field Poisson-Boltzmann
description for the microscopic electrolyte ions with a Brownian-dynamics
simulation for the mesoscopic colloids. This technique ensures that many-body
interactions between the colloids are fully taken into account, and thus allows
us to investigate how many-body interactions affect the solid-liquid phase
behavior of charged colloids. Using the Lindemann criterion, we determine the
melting line in a phase-diagram spanned by the colloidal charge and the salt
concentration. We compare our results to predictions based on the established
description of colloidal suspensions in terms of pairwise additive Yukawa
potentials, and find good agreement at high-salt, but not at low-salt
concentration. Analyzing the effective pair-interaction between two colloids in
a crystalline environment, we demonstrate that the difference in the melting
behavior observed at low salt is due to many-body interactions
Cell surface antigen expression by peripheral blood monocytes in allergic asthma: results of 2.5 years therapy with inhaled beclomethasone dipropionate
At present, inhaled glucocorticoids are widely accepted as the therapy of choice in chronic asthma. Treatment with inhaled glucocorticoids significantly suppresses local airway inflammation in asthmatics, but may also have systemic effects, e.g. a reduction of the number of circulating hypodense eosinophils or a down-modulation of HLA-DR antigen (Ag) expression by T lymphocytes in peripheral blood. However, the effect of long-term therapy with inhaled glucocorticoids on peripheral blood monocytes (PBM), which are the precursors of the most numerous cell type in the lung, the alveolar macrophage, have not yet been evaluated. We therefore investigated the expression of various cell surface Ag on PBM from non-smoking patients with allergic asthma who were treated for 2.5 years with a β2-receptor agonist plus either an inhaled glucocorticoid (beclomethasone dipropionate, BDP) (n = 4) or an anticholinergic or placebo (n = 8). We compared the results with healthy volunteers (n = 7). Long-term treatment of allergic asthmatics with inhaled BDP, but not anticholinergic or placebo therapy, was associated with a significantly lower CDllb Ag expression (p < 0.04) and higher expression of CD13, CD14 and CD18 Ag (p < 0.05, p < 0.02 and p < 0.04, respectively) when compared with the healthy control subjects (n = 7). Most interestingly, PBM of asthmatics treated with inhaled BDP expressed an almost two-fold higher level of CD14 Ag on their cell surface than PBM of patients treated with anticholinergic or placebo (p < 0.03). No significant differences in the expression of CD16, CD23, CD25, CD32 and CD64 Ag or HLA-DR were observed between PBM from the different patient groups or healthy controls. Taken together, this study shows that long-term local therapy with inhaled BDP coincides with an altered expression of at least one cell surface Ag on PBM from allergic asthmatics
Paediatric obsessive-compulsive disorder and depressive symptoms: clinical correlates and CBT treatment outcomes.
Depression frequently co-occurs with paediatric obsessive-compulsive disorder (OCD), yet the clinical correlates and impact of depression on CBT outcomes remain unclear. The prevalence and clinical correlates of depression were examined in a paediatric specialist OCD-clinic sample (N = 295; Mean = 15 [7 - 18] years, 42 % female), using both dimensional (Beck Depression Inventory-youth; n = 261) and diagnostic (Development and Wellbeing Assessment; n = 127) measures of depression. The impact of depressive symptoms and suspected disorders on post-treatment OCD severity was examined in a sub-sample who received CBT, with or without SSRI medication (N = 100). Fifty-one per-cent of patients reported moderately or extremely elevated depressive symptoms and 26 % (95 % CI: 18 - 34) met criteria for a suspected depressive disorder. Depressive symptoms and depressive disorders were associated with worse OCD symptom severity and global functioning prior to CBT. Individuals with depression were more likely to be female, have had a psychiatric inpatient admission and less likely to be attending school (ps < 0.01). OCD and depressive symptom severity significantly decreased after CBT. Depressive symptoms and depressive disorders predicted worse post-treatment OCD severity (βs = 0.19 and 0.26, ps < 0.05) but became non-significant when controlling for pre-treatment OCD severity (βs = 0.05 and 0.13, ns). Depression is common in paediatric OCD and is associated with more severe OCD and poorer functioning. However, depression severity decreases over the course of CBT for OCD and is not independently associated with worse outcomes, supporting the recommendation for treatment as usual in the presence of depressive symptoms
The osmotic pressure of charged colloidal suspensions: A unified approach to linearized Poisson-Boltzmann theory
We study theoretically the osmotic pressure of a suspension of charged
objects (e.g., colloids, polyelectrolytes, clay platelets, etc.) dialyzed
against an electrolyte solution using the cell model and linear
Poisson-Boltzmann (PB) theory. From the volume derivative of the grand
potential functional of linear theory we obtain two novel expressions for the
osmotic pressure in terms of the potential- or ion-profiles, neither of which
coincides with the expression known from nonlinear PB theory, namely, the
density of microions at the cell boundary. We show that the range of validity
of linearization depends strongly on the linearization point and proof that
expansion about the selfconsistently determined average potential is optimal in
several respects. For instance, screening inside the suspension is
automatically described by the actual ionic strength, resulting in the correct
asymptotics at high colloid concentration. Together with the analytical
solution of the linear PB equation for cell models of arbitrary dimension and
electrolyte composition explicit and very general formulas for the osmotic
pressure ensue. A comparison with nonlinear PB theory is provided. Our analysis
also shows that whether or not linear theory predicts a phase separation
depends crucially on the precise definition of the pressure, showing that an
improper choice could predict an artificial phase separation in systems as
important as DNA in physiological salt solution.Comment: 16 pages, 5 figures, REVTeX4 styl
Shear Thickening Creep in Superplastic Silicon Nitride
Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65512/1/j.1151-2916.1992.tb05540.x.pd
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