The double layer and ion adsorption at the interface between two non miscible solutions: Part I. Interfacial tension measurements for the water-nitrobenzene tetraalkylammonium bromide systems

The classical treatment of the double layer has been extended to the interface between two immiscible solutions. The model presented is composed of an inner compact layer, characterized by a dipolar potential drop, between two diffuse type layers. The systems studied are composed of C₂ to C₅ quaternary ammonium bromides at partition equilibrium between water and nitrobenzene for which the inner potential difference, for a given electrolyte, is independent, at least in the lower concentration range, of the concentration. Drop weight interfacial measurements and the use of the Gouy-Chapman approach show that the tetraethyl-, tetrapropyl- and tetrabutylammonium ions are not adsorbed within the inner compact layer, and the dipolar potential drop of this layer can then be determined. Tetrapentylammonium ions on the contrary are specifically adsorbed but the amount of adsorbed ions within the compact inner layer cannot be evaluated because of the impossibility, in this case, of determining the dipolar potential drop.     

PHOTOINDUCED VOLTA POTENTIAL IN A PORPHYRIN MONOLAYER

Abstract— When spread on an oxidizing aqueous subphase, an amphipathic basket handle zinc porphyrin (P) monolayer gives rise to a photoinduced Volta potential change. This surface photopotential is interpreted on the basis of an interfacial electron transfer in the interphase; upon light excitation, electrons are transferred from the chromophores in the monolayer to electron acceptors diffusing from the subphase. A kinetic model for charge separation and stabilization is proposed to account for the influences of the electron acceptor concentration, the pH of the subphase and the light intensity.     

A potentiostatic study of hydrophobic ion transfer across lipid bilayer membranes: Part II. Transport of tetraphenylborate ions at high concentration in the aqueous solution

The transfer of tetraphenylborate (TPB^?) ions across black lipid membranes in aqueous solutions ranging from 10^?5M to 10^?3M, has been studied under potentiostatic conditions. A theoretical treatment of the problem accounts for the two time constants given and for the diffusion current for prolonged periods of time if one assumes that the adsorption-desorption transfer currents are large. This is tantamount to considering that these two processes are highly reversible and that the dipolar nature of the drop in potential between the closest approach and adsorption planes determines the adsorption. The resistances corresponding to the translocation and adsorption-desorption processes have thus also been evaluated. Using these results and those given by surface potential measurements on monolayers of glycerylmono-oleate, the number of adsorbed ions has been calculated. This has led to an explanation of the well known conductance maximum encountered when the concentration of the tetraphenylborate ions varies.     

Polymer inclusion membranes: The concept of fixed sites membrane revised

The mechanism of facilitated transport of metal ions across polymer inclusion membranes (PIMs) is revised on the basis of transport flux measurements and of new data brought by techniques sensitive to local inter-molecular interactions and molecular diffusion. Cellulose triacetate (CTA) membranes built with two types of inclusion carriers: a liquid one Aliquat 336 and a crystalline one Lasalocid A, both able to carry metal ions across PIMs and supported liquid membranes (SLMs) made of the same components, have been compared. Both PIM systems show similar effects for what concern the need of a carrier threshold concentration for the occurrence of a transport flux across PIM as revealed by flux and fluorescence correlation spectroscopy (FCS) measurements, and the dependence of the chemical nature of plasticizers on the metal ion flux. These systems also present similar Raman and far IR signatures of structural evolution of PIMs with the increase of the carrier concentration within the CTA matrix.

All the presented data are interpreted as concern PIMs, according to an evolution of chemical interactions between components of the polymeric membrane able to lead to a phase transition. This phase transition type of the carrier-plasticized polymer system is induced by the increase of carrier concentration in the polymer chains. The PIM progressively organizes itself like a liquid SLM because of the enhancement of preferential solvent interactions between the carrier and the plasticizer.

The main conclusion of this study is that the classically adopted “hopping” transport mechanism between fixed carrier sites in a PIM does not apply to such carrier chemically unbound to polymer membrane systems.     

Removal of lead and cadmium ions from aqueous solution by adsorption onto micro-particles of dry plants

In the present work, Pb(II) and Cd(II) ion adsorption onto inert organic matter (IOM) obtained from ground dried plants: Euphorbia echinus, Launea arborescens, Senecio anthophorbium growing in semi-arid zones of Morocco and Carpobrotus edulis as the Mediterranean plant has been studied. A suspension of plant deroed micro-particles adsorbs lead and cadmium present as ionic species, with a higher affinity for Pb(II). The kinetics and the maximum capacity adsorption depend on the type of plant as well as on the metal ions (atomic weight, ionic radius and electronegativity). The adsorption process is affected by various parameters such as contact time, solution volume to mass of plant particles ratio (m/V), particle size, solution pH and metal concentration. A dose of 25 g/l of adsorbent was optimal to obtain maximum adsorption of both metal ions. The maximum metal uptake was obtained with particles of organic matter of <50 microm. As to classical ionic adsorption phenomena, the adsorption of both metal ions increases with the increase of the initial concentration in the solution. For the two metal cations, the uptake efficiency of the studied plants ranged from: C. edulis>E. echinus>S. anthophorbium>L. arborescens, however, the differences are rather small. Two different waste water types (domestic and industrial) were tested and good results were obtained for removal of Pb(II) and Cd(II) at more than 90%. The removal of the metal and mineral ions waste water was observed for PO(4)(3-) at 88%, for NO(3)(-) at 96.5% and for metal ions (Pb(II), Cd(II), Cu(II) and Zn(II)) at about 100%, using IOM as absorbent.     

Facilitated Cd(II) transport across CTA polymer inclusion membrane using anion (Aliquat 336) and cation (D2EHPA) metal carriers

PIMs have been involved as affinity membranes for recovery of metals (Cd, Pb, Zn) by facilitated transport from aqueous solutions under different speciation forms, either anionic or cationic. The motivation of this work is to compare the efficiency of the recovery process in the case of Cd(II) using extractants such as D2EHPA and Aliquat 336 that can form complexes with the cation Cd²⁺ or the anions CdCl₃⁻ and CdCl₄²⁻, respectively. The maximal Cd(II) recovery factors obtained in 8 h are 97.5% and 91.8% with D2EHPA and Aliquat 336, respectively. Although the transport fluxes with both carriers are not strongly different (ca. 2 μmol m⁻² s⁻¹), the recovery process in case of mixture of metals is better achieved with Aliquat 336. PIMs have shown a very good stability and a constancy of the transmembrane transport flux over 12 replicate measurements, each one lasting for 8 h repeated every 24 h.     

The double layer and ion adsorption at the interface between two immiscible solutions: Part III. Long chain alkyl-trimethylammonium halides at partition equilibrium between water and nitrobenzene

The surface excesses of alkyltrimethylammonium halides have been evaluated from interfacial surface tension measurements carried out at the partition equilibrium between water and nitrobenzene.The model considered is constituted by two space charge layers on either side of a central compact layer which contains alkyltrimethylammonium ions arranged as in an adsorbed monolayer.The value of the electrical potential at the junction plane between the two phases depends on the degree of dissociation within the inner layer and on the number of specifically adsorbed ions. If one assumes complete dissociation it is possible to establish the variation of the adsorption isotherms with the chemical and electrical parameters and thus determine the value of the free energy of adsorption with the number of CH₂ groups in the alkyl chain.The results obtained do not indicate an important effect due to the counter ion, which would tend to substantiate the hypothesis of a total dissociation within the central layer.Furthermore the fact is stressed that the knowledge of the isotherm depends on the magnitude of the potential drop within the compact layer, the value of which cannot be determined by purely thermodynamical measurements.     

A potentiostatic study of hydrophobic ion transfer across lipid bilayer: Part I. Case of zero ion fluxes in adsorption and desorption processes

The transport of tetraphenylborate (TPB^?) and dipicrylamine (DPA^?) ions across glyceryl monoleate decane bilayers is studied under potentiostatic conditions. The transfer mechanism involving three steps (adsorption-translocation-desorption) is retained with the modification that the adsorbed charge, due to the transfer of ions, is taken into consideration. This threecapacitor B.L.M. model enables one to prodict, as is experimentally established, that the electrical driving force of the translocation process is only a fraction of the total applied voltage. In the particular case where the ion fluxes in the adsorption and desorption steps are negligible with respect to the capacitive current, the values of the translocation rate constant, the number of adsorbed ions and the adsorption and desorption capacitance are estimated from the current-time response curves.     

The LUMO-derived band of the [Formula: see text] phases

The LUMO-derived band of the [Formula: see text] compound was investigated by means of x-ray and UV photoemission and photoelectric yield spectroscopies. A double-peak structure is found, with peak maxima at 1.1 eV and 0.35 eV. The relative magnitude of the two peaks is strongly temperature dependent: a large transfer of spectral weight from the lower- to the higher-binding-energy peak takes place upon cooling to 110 K. The peaks are tentatively attributed to the dimer and the polymeric phase respectively. However the behaviour as a function of temperature does not agree with the metastability of the dimer phase at room temperature. The position of the Fermi level is compatible with a correlated system on the border of the metal - insulating transition.     

Electrospun Nanofibers Modified with Phospholipid Moieties for Enzyme Immobilization

Summary: PANCMPCs containing phospholipid side moieties were electrospun into nanofibers with a mean diameter of 90 nm. Field emission SEM was used to characterize the morphologies of the nanofibers. These phospholipid‐modified nanofibers were explored as supports for enzyme immobilization due to the characteristics of excellent biocompatibility, high surface/volume ratio, and porosity, which were beneficial to the catalytic efficiency and activity of immobilized enzymes. Lipase from Candida rugosa was immobilized on these nanofibers by adsorption. Preliminary results indicated that the properties of the immobilized lipase on these phospholipid‐modified nanofibers were greatly promising.

Schematic representation of the structure and electrostatic properties of phospholipid‐modified nanofibers.