Irreversible thermodynamics of transport across charged membranes : Part I — Macroscopic resistance coefficients for a system with nafion 120 membrane

The transport of aqueous NaCl solutions across the perfluorinated Nafion 120 membrane is studied on the base of irreversible thermodynamics. The straight resistance coefficients r_ii, partial frictions f_ik^p and diffusion indices RT/c?_ir_ii are presented and discussed. The results suggest that the main force, which impedes the flow of chloride ions across the membrane is not the friction of these ions with the negatively charged polymer network, but the friction with water. The diffusion indices RT/c?_ir_ii exceed self-diffusion coefficients found by some authors while using tracer technique. Following Meares' suggestion such results point out to the convective flow contribution to the transport of ions and water.     

Irreversible thermodynamics of transport across charged membranes : Part II-ion-water interactions in permeation of alkali

The detailed analysis of membrane phenomena in the system Nafion 120 membrane/NaOH_aq at 298, 313 and 3n33 K has been performed, taking for discussion the phenomenological transport coefficients r_ii, f_ik and diffusion indices D̄_i^r. Comparing the numerical values found here with the corresponding data determined for the system with NaCl solutions it is shown that cation-anion frictional force, which is usually assumed zero, cannot be neglected for the Na⁺-OH⁻ pair of ions. These interactions influence diffusional and osmotic transport of a solute and water across the membrane. Another specific effect of OH⁻ ions important for membrane permeation is the very low friction of OH⁻ ions with water.     

Viscous flow and non-linear phenomena in non-equilibrium thermodynamics of membrane transport Part 2 — The phenomenological equations

Phenomenological equations are deduced which give the flows of matter, volume, charge and heat for a discontinuous system in which inertial terms in the viscous equations of motion are not negligible. It is found that the equations contain terms in the powers of the first-order affinities, with corresponding phenomenological coefficients. These coefficients can all be derived from first-order coefficients, however, and thus refer to a system which is close to equilibrium. The theory agrees with well-documented specific hydrodynamic calculations, but generalizes these in the framework of now equilibrium thermodynamics.     

Electrokinetic phenomena in porous membranes: Determination of phenomenological coefficients and transport numbers

Electrokinetic phenomena in porous membranes were studied in the framework of the linear thermodynamics of irreversible processes. Phenomenological coefficients of two commercial porous membranes were determined. The variation of these coefficients with the different concentrations of NaCl used was also studied. Onsager's reciprocal relationship between cross-coefficients holds within the limits of experimental error.Membrane potentials were measured at concentrations ranging from 10^?3M to 75 X 10^?3M. The apparent transport number of the cation,

, was calculated from the diffusion potential expression. An electrometric method was used to obtain the true cation transport number,

, and the water transport number,

, for different solution concentrations, ranging from 15 x 10^?3M to 75 x 10^?3M. The true transport number of the cation,

, was also determined, taking into account water transport across the membrane. A good agreement was found between

and

values.     

Solubility-based gas separation with oligomer-modified inorganic membranes: Part III. Effects of synthesis conditions

As in previous papers in this series, we created membranes for solubility-based gas separations by reacting the surfaces of microporous alumina substrates with alkylchlorosilanes. In this paper, we explored our ability to rationally modify the permselectivity properties of these membranes through the control of several synthesis variables. In particular, we studied three different hydration states of the alumina surface (dehydrated, normal, and superhydrated), two different degrees of chlorosilane functionality (mono and tri), and two different sizes of alkyl group (methyl and octadecyl). We measured the permeability of the hybrid membranes to propane and nitrogen gases to characterize their separation properties; we also carried out X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) experiments to characterize the amount and nature of organic surface coverage. Our results showed significant correlations of permeation properties with all of the synthesis variables. Dehydration of the alumina surface before trichlorosilane treatment resulted in a lower organic surface coverage and a lower propane/nitrogen selectivity; superhydration resulted in the formation of a dense organic surface layer with a large number of macroscopic defects that virtually eliminated selectivity. Under normal hydration conditions, the octadecyltrichlorosilane yielded a far more selective membrane than the methyltrichlorosilane. Finally, the monochlorosilane reagents produced no significant organic surface coverage, based on both XPS and gas permeation analyses. We discuss our results in the context of previous work on (1) self-assembled monolayers on nonporous substrates and (2) the design of solubility-selective membranes.     

A spray technique for the determination of membrane diffusion and distribution coefficients by the time-lag method: evaluated for electrolyte transport through charged and uncharged membranes

Using solution sprays, a sharp concentration step may be effected at the surface of a membrane in less than 0.1 sec. This technique allows the time-lag method to be used to determine rapidly both solute permeability and diffusion coefficient in a single experiment. From the mathematical analysis of diffusion into a cell with finite collecting volume, limiting conditions are derived which define experimental conditions under which the conventional linear, steady state analysis of time lag will be valid. These limiting conditions were used to determine the dimensions of the experimental diffusion cell. Diffusion, permeability and distribution coefficients were measured for a variety of electrolytes in both charged and uncharged membranes and shown to be in good agreement with conventional methods. A Donnan analysis is given by which the charged nature of an unknown membrane may be assessed precisely and rapidly.     

A novel positively charged asymmetry membranes from poly(2,6-dimethyl-1,4-phenylene oxide) by benzyl bromination and in situ amination: Part II: Effect of charged group species on membrane performance and morphologies

Positively charged membrane with various charged groups were prepared by in situ amination and phase inversion in which the amine-organic solution and bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) was cast and immerged into an ethanol coagulation bath. The separation performance and morphologies were examined to investigate the effect of hydrophilicity of charged groups on the selective properties and the structure formation of the membranes. Positively charged groups introduced in the membranes were trimethylbenzylammonium, triethylbenzylammonium, tri-n-propylbenzylammonium and tri-n-butylbenzylammonium, in order of increasing hydrophobicity. Pure water flux and rejection to gelatin of the membranes at three pH values changed remarkably with increasing chain length of alkyl groups. The tendency of the change was mainly explained by coagulation value of the casting solution. The streaming potential and ion exchange capacity of the membranes were determined and the results showed that the membranes were all positively charged. Furthermore, water content, pore size distribution and SEM images of the membranes were examined as well.     

Folding and self-association of atTic20 in lipid membranes: implications for understanding protein transport across the inner envelope membrane of chloroplasts

Background

We have previously shown that the P. gingivalis HmuY hemophore-like protein binds heme and scavenges heme from host hemoproteins to further deliver it to the cognate heme receptor HmuR. The aim of this study was to characterize structural features of HmuY variants in the presence and absence of heme with respect to roles of tryptophan residues in conformational stability.

Results

HmuY possesses tryptophan residues at positions 51 and 73, which are conserved in HmuY homologs present in a variety of bacteria, and a tryptophan residue at position 161, which has been found only in HmuY identified in P. gingivalis strains. We expressed and purified the wildtype HmuY and its protein variants with single tryptophan residues replaced by alanine or tyrosine residues. All HmuY variants were subjected to thermal denaturation and fluorescence spectroscopy analyses. Replacement of the most buried W161 only moderately affects protein stability. The most profound effect of the lack of a large hydrophobic side chain in respect to thermal stability is observed for W73. Also replacement of the W51 exposed on the surface results in the greatest loss of protein stability and even the large aromatic side chain of a tyrosine residue has little potential to substitute this tryptophan residue. Heme binding leads to different exposure of the tryptophan residue at position 51 to the surface of the protein. Differences in structural stability of HmuY variants suggest the change of the tertiary structure of the protein upon heme binding.

Conclusions

Here we demonstrate differential roles of tryptophan residues in the protein conformational stability. We also propose different conformations of apo- and holoHmuY caused by tertiary changes which allow heme binding to the protein.     

Viscous flow and non-linear phenomena in non-equilibrium thermodynamics of membrane transport : Part 1 — The rate of entropy production for a discontinuous steady-state system

The rate of entropy production is calculated by a method of de Groot and Mazur for a discontinuous system consisting of a small subsystem (membrane, capillary or porous diaphragm) in contact with two larger uniform subsystems. The velocity can vary with position (spatial acceleration) in the smaller system, but steady state conditions prevail (velocity independent of time). In the larger subsystems, the velocity is independent of position, but can vary with time. Inertial terms in the equation of motion, kinetic energy of diffusion and polarization terms are included systematically. The resulting equation for the rate of entropy production shows that contributions from (1) kinetic energy of diffusion, (2) barycentric kinetic energy, (3) polarization forces, (4) work done by viscous forces and (5) chemical reactions, each averaged over the small subsystem, appear automatically. The first contribution gives a term in the squares of the mass flows relative to the centre of mass, the “kinetic diffusion effect”. The second and third contributions give a corrected pressure affinity which contains terms in the square of the volume flux and the square of the electric potential difference, while the fourth is incorporated into the volume flow and the fifth is generally negligible. The results provide a thermodynamic basis for non-linear terms in the transport equations, clarify the meaning of steady state as applied to membrane transport, and also clarify the relation between average flow quantities and those flow properties which are observable in the larger subsystems.     

The application of salicylaldoxime in solvent extraction : Part II. Spectrophotometric determination of copper with 2-(5-nitro-2-pyridylazo)-1-naphthol after separation with salicylaldoxime

A highly sensitive spectrophotometric method for the determination of traces of copper with 2-(5-nitro-2-pyridylazo)-l-naphthol (5N-α-PAN) has been developed. At a pH of 3–4copper(II) is selectively extracted into chloroform as its salicylaldoxime chelate and then stripped into an aqueous acid solution; the pH is adjusted to 9.3, and 5N-α-PAN is added. The 1:2 chelate between copper(II) and the reagent, which promptly precipitates, is extracted into chloroform and measured at 598 nm. The molar absorptivity is 86,000. The application of the method to the analysis of high-purity magnesium and cobalt is described.     

Linear free energy relationships and kinetics of ligand substitutions: Correlations of rate constants with overall stability constants of reactive intermediate species in the stepwise formation of pentacyanohydroxoferrate(III) from monohydroxoaminocarboxylato iron(III) complexes

Summary A linear free energy relationship has been proposed between stepwise rate constants and the overall stability constants of the intermediates of the type FeL(OH)(CN)_x (where x=0, 1, 2 and 3) formed in the five step reaction mechanism of CN^– with FeLOH, where L denotes aminocarboxylatesviz. EDTA, HEDTA and DTPA.     

Structural and photophysical properties of coordination networks combining [Ru(Bpym)(CN)4]2- or [[Ru(CN)4]2(mu-bpym)]4- anions (bpym = 2,2'-bipyrimidine) with lanthanide(III) cations: sensitized near-infrared luminescence from Yb(III), Nd(III), and Er(III) following Ru-to-lanthanide energy transfer

Reaction of the cyanoruthenate anions [Ru(bpym)(CN)4]2- and [[Ru(CN)4]2(mu-bpym)]4- (bpym = 2,2'-bipyrimidine) with lanthanide(III) salts resulted in the crystallization of coordination networks based on Ru-CN-Ln bridges. Four types of structure were obtained: [Ru(bpym)(CN)4][Ln(NO3)(H2O)5] (Ru-Ln; Ln = Sm, Nd, and Gd) are one-dimensional helical chains; [Ru(bpym)(CN)4]2[Ln(NO3)(H2O)2][Ln(NO3)(0.5)(H2O)(5.5)](NO3)(0.5).5.5H2O (Ru-Ln; Ln = Er and Yb) are two-dimensional sheets containing cross-linked chains based on Ru2Ln2(mu-CN)4 diamond units, which are linked into one-dimensional chains via shared Ru atoms; [[Ru(CN)4]2(mu-bpym)][Ln(NO3)(H2O)5]2.3H2O (Ru2-Ln; Ln = Nd and Sm) are one-dimensional ladders with parallel Ln-NC-Ru-CN-Ln-NC strands connected by the bipyrimidine "cross pieces" acting as rungs on the ladder; and [[Ru(CN)4]2(mu-bpym)][Ln(H2O)6](0.5)[Ln(H2O)4](NO3)(0.5).nH2O (Ru2-Ln; Ln = Eu, Gd, and Yb; n = 8.5, 8.5, and 8, respectively) are three-dimensional networks in which two-dimensional sheets of Ru2Ln2(mu-CN)4 diamonds are connected via cyanide bridges to Ln(III) ions between the layers. Whereas Ru-Gd shows weak triplet metal-to-ligand charge-transfer (3MLCT) luminescence in the solid state from the Ru-bipyrimidine chromophore, in Ru-Nd, Ru-Er, and Ru-Yb, the Ru-based emission is quenched, and all of these show, instead, sensitized lanthanide-based near-IR luminescence following a Ru --> Ln energy transfer. Similarly, Ru2-Nd and Ru2-Yb show lanthanide-based near-IR emission following excitation of the Ru-bipyrimidine chromophore. Time-resolved luminescence measurements suggest that the Ru --> Ln energy-transfer rate is faster (when Ln = Yb and Er) than in related complexes based on the [Ru(bipy)(CN)4]2- chromophore, because the lower energy of the Ru-bpym 3MLCT provides better spectroscopic overlap with the low-energy f-f states of Yb(III) and Er(III). In every case, the lanthanide-based luminescence is relatively short-lived as a result of the CN oscillations in the lattice.