Epameinondas Leontidis

Hofmeister anion effects on surfactant self-assembly and the formation of mesoporous solids

Recent work on mesoporous silica formation using cationic and non-ionic templates has unveiled a large number of anion effects. Anions are seen to change the hydrolysis rates of the silicate precursors, affecting the surface properties and morphologies of the final products after calcination, and they often improve the hydrothermal stability of the silica materials. These advances are reviewed in connection with the Hofmeister series of anions and the known effects of anions on the self-assembly and phase behavior of cationic and non-ionic surfactants.

Liquid Expanded Monolayers of Lipids As Model Systems to Understand the Anionic Hofmeister Series: 1. A Tale of Models

In this work, we use Langmuir monolayers of dipalmitoyl phosphatidylcholine (DPPC) as model systems to enhance the understanding of specific anion effects in physicochemical and biological systems. The 298 K isotherms (equation of state, EOS) of DPPC over solutions of a range of sodium salts depend strongly on the type and concentration of the salt in the subphase. We focus in particular on the liquid expanded phase region of the DPPC EOS and assume that the deviation of the isotherms over electrolyte solutions from that over pure water is due entirely to the charging of the lipid monolayer by the ions. We then examine the ability of a range of phenomenological continuum models to explain the pressure increase in the presence of electrolytes. The important finding is that insoluble lipid monolayers allow the discrimination between possible modes of ion-lipid interaction. Chemical binding models, simple or modified, cannot fit the range of data presented in this work. Both dispersion interaction and partitioning models fit most of the experimental isotherms and provide unique values for dispersion coefficients or ionic partitioning constants, respectively, even though the nature of these models is completely different (the former concentrates on the potential of mean force that acts on an ion in the double layer, while the latter concentrates on the treatment of interactions at the interface). Surprisingly, the respective fitting parameters are very highly correlated, reflecting, we believe, the effect of ion size on ionic properties and interactions. With sodium fluoride (NaF) as the subphase electrolyte, it is demonstrated that sodium exhibits a weak complexation-type interaction with the zwitterionic lipids. The simple dispersion and partitioning models cannot account for the NaF results, highlighting the need for more complex salt-lipid interaction models that account both for sodium binding and anion partitioning. This realization sets the stage for the companion paper.

Liquid expanded monolayers of lipids as model systems to understand the anionic hofmeister series: 2. Ion partitioning is mostly a matter of size.

In the preceding paper of this series [ Leontidis , E. ; Aroti , A. ; Belloni , L. J. Phys. Chem. B 2009 , 113 , 1447 ], we considered and modeled the increase of the surface pressure of dipalmitoyl phosphatidylcholine (DPPC) monolayers over electrolyte solutions of various monovalent sodium salts. The experimental results for salts with large, less hydrophilic anions can be successfully described by models treating ionic specificity either as specific partitioning in the interfacial lipid layer or as a result of ion-lipid dispersion interactions. However, the results for salts with more hydrophilic anions, such as chloride and fluoride, cannot be fitted by any of these models, while they clearly demonstrate the existence of a specific sodium-DPPC interaction. In the present paper, we first prove that the experimental results for sodium fluoride (NaF) can be fitted by a model that is based on simultaneous complexation of sodium ions with up to three lipid molecules, as suggested by recent molecular dynamics simulations. We then return to the experimental results of sodium salts with more hydrophobic anions, treated in the preceding paper, and prove that these can be fitted equally well with a complex model, which accounts for both sodium complexation with the lipid head groups and anion partitioning within the lipid monolayers. The partitioning parameters obtained from this more complete model correlate well with several measures of ion specificity, such as ionic volume, von Hippel chromatographic parameters, or viscosity B-coefficients. A model for these partitioning chemical potentials is created based on the competition of cavity and ion hydration terms. The model leads to an excellent correlation of the partitioning chemical potentials with a function of the ionic radius, suggesting that specific anion effects on this lipid model system are mostly a matter of ionic size. Two notable exceptions from this correlation are thiocyanate and acetate ions, the charge distribution of which is not spherically symmetric, so that they are expected to have orientational-dependent interactions with the water-lipid interface. The implications of the present results on ion specificity in general are discussed.

Vibrational sum frequency generation spectroscopic investigation of the interaction of thiocyanate ions with zwitterionic phospholipid monolayers at the air-water interface.

Thiocyanate (SCN(-)) is a highly chaotropic anion of considerable biological significance, which interacts quite strongly with lipid interfaces. In most cases it is not exactly known if this interaction involves direct binding to lipid groups, or some type of indirect association or partitioning. Since thiocyanate is a linear ion, with a considerable dipole moment and nonspherical polarizability tensor, one should also consider its capability to adopt different or preferential orientations at lipid interfaces. In the present work, the interaction of thiocyanate anions with zwitterionic phospholipid monolayers in the liquid expanded (LE) phase is examined using surface pressure-area per molecule (pi-A(L)) isotherms and vibrational sum frequency generation (VSFG) spectroscopy. Both dipalmitoyl phosphatidylcholine (DPPC) and dimyristoyl phosphatidylethanolamine (DMPE) lipids, which form stable monolayers, have been used in this investigation, since their headgroups may be expected to interact with the electrolyte solution in different ways. The pi-A(L) isotherms of both lipids indicate a strong expansion of the monolayers when in contact with SCN(-) solutions. From the C-H stretch region of the VSFG spectra it can be deduced that the presence of the anion perturbs the conformation of the lipid chains significantly. The interfacial water structure is also perturbed in a complex way. Two distinct thiocyanate populations are detected in the CN stretch spectral region, proving that SCN(-) associates with zwitterionic phospholipids. Although this is a preliminary investigation of this complex system and more work is necessary to clarify certain points made in the discussion, a potential identification of the two SCN(-) populations and a molecular-level explanation for the observed effects of the SCN(-) on the VSFG spectra of the lipids is provided.

Monte Carlo algorithms for the atomistic simulation of condensed polymer phases

Significant progress has been made recently in the field of atomistic simulation of polymer melts through the advent of new powerful Monte Carlo methods. This article reviews the state of the art in the area. Sampling the configurational space of a dense polymer system is difficult, because of complications introduced by high density and the connectivity of the chain molecules. We describe how some novel algorithms attempt to solve the problem, compare them using a set of stringent performance criteria and discuss their strengths and their weaknesses, their successes and their failures. Although we have still not reached the stage where realistically long polymeric chains with atomistic detail can be treated successfully, there is ground for hope. Configuration-bias Monte Carlo (CBMC) and its extensions, concerted-rotation (ConRot)-based algorithms, and hybrid Monte Carlo (HMC) have opened up new possibilities for the investigation of more realistic polymer models than the ones used hitherto. The field of possible applications is vast: studies of polymers in melts and in solution, prediction of single-phase thermodynamic properties and phase equilibria, biopolymer modelling and, hopefully, the long-time behaviour of macromolecular systems, may soon become tractable with the rapid evolution of novel Monte Carlo methods.

Effects of Sodium Salts of Lyotropic Anions on Low-Temperature, Ordered Lipid Monolayers

Electrolytes are known to impart considerable disorder to lipid assemblies, including monolayers at the air-water interface, bilayers, and vesicles. In the present work, we have investigated the disordering effect of sodium salts of monovalent anions that span the lyotropic series on the monolayers of 1,2-dipalmitoyl-sn-glycero-phosphocholine (DPPC) at 12 °C. Pressure-area isotherms, Brewster-angle microscopy (BAM), grazing-incidence X-ray diffraction (GIXD), and infrared absorption-reflection spectroscopy (IRRAS) were used to investigate in complementary ways the salt effects on lipid monolayers. At 12 °C these effects were found to be quite dramatic, a major finding being that the liquid-expanded phase, which is not present at this temperature on a pure water subphase, reappears and dominates in the presence of electrolytes. Salts expand the monolayer, destroy the ordered phase that exists at zero pressure, and affect the ordering of the lipid chains and their tilt angle in the liquid condensed phase. Finally, very chaotropic anions force DPPC lipids to adopt an untilted conformation in the condensed phase, an unprecedented finding for nonmixed Langmuir monolayers of this phospholipid. A distinctly different behavior of very chaotropic anions from that of normal chaotropic ones thus emerges. The effect of the former is not just a limited perturbation of the lipid assembly but a major disruption of the structure, which arises from competition between the lipids and the ions for interfacial sites.

Stabilization of Lead Sulfide Nanoparticles by Polyamines in Aqueous Solutions. A Structural Study of the Dispersions

Lead sulfide (PbS) nanoparticles have been synthesized in aqueous solutions by a reaction between inorganic lead salts and sodium sulfide and stabilized using the cationic polyelectrolytes branched poly(ethylenimine) (PEI), poly(allylamine hydrochloride) (PAH), and poly(diallyldimethylammonium chloride) (PDDA). The structures of the polyamine-stabilized nanoparticle dispersions were examined in detail using UV-vis spectroscopy, small-angle X-ray scattering (SAXS), static and dynamic electrophoretic mobility measurements, and transmission electron microscopy (TEM). Considerable differences were found between the stabilizing efficiencies of these polyelectrolytes, which cannot be attributed to their charge densities or their persistence lengths. Small monodisperse nanoparticles of PbS with a tight stabilizing shell were consistently found only when PEI was used as a stabilizer even at high pH values, although its charge density is then very low. The excellence of PEI as a stabilizer is mainly due to the extensive branching of the chains and the presence of uncharged secondary and tertiary amine groups, which apparently serve as good anchoring points at the nanoparticle surfaces. None of the polyelectrolytes examined here provide long-term protection of the nanoparticles toward oxidation by air, showing that a need for more complex multipurpose stabilizers exists for aqueous PbS dispersions.

Bound states in a nonlinear Kronig - Penney model

We study the bound states of a Kronig Penney potential for a nonlinear one-dimensional Schrodinger equation. This potential consists of a large, but not necessarily infinite, number of equidistant -function wells. We show that the ground state can be highly degenerate. Under certain conditions furthermore, even the bound state that would normally be the highest can have almost the same energy as the ground state. This holds for other simple periodic potentials as well.

The Shpol’skii system perylene in n-hexane: A computational study of inclusion sites

We present a combined quantum mechanics/molecular mechanics study of the Shpol’skii system perylene/n-hexane. The system was modeled utilizing a customized pcff-derived force field optimized with a balanced set of optimization criteria based on geometry, vibrational modes, and the energies and forces in an ensemble of molecular geometries. Spectral shifts were calculated perturbatively using the method of Shalev et al. [J. Chem. Phys. 95, 3147 (1991)]. The calculated shifts are within the experimental uncertainty of the observed 0–0 lines and allow an unambiguous assignment of the three most prominent sites. The proposed assignment differs from that of a previous study.

Investigations of the Hofmeister series and other specific ion effects using lipid model systems

From the ion point-of-view specific ion effects (SIE) arise as an interplay of ionic size and shape and charge distribution. However in aqueous systems SIE invariably involve water, and at surfaces they involve both interacting surface groups and local fields emanating from the surface. In this review we highlight the fundamental importance of ionic size and hydration on SIE, properties which encompass all types of interacting forces and ion-pairing phenomena and make the Hofmeister or lyotropic series of ions pertinent to a broad range of systems and phenomena. On the other hand ionic hydrophobicity and complexation capacity also determine ionic behavior in a variety of contexts. Over the years we have carried out carefully designed experiments on a few selected soft matter model systems, most involving zwitterionic phospholipids, to assess the importance of fundamental ionic and interfacial properties on ion specific effects. By tuning down direct Coulomb interactions, working with different interfacial geometries, and carefully tuning ion-lipid headgroup interactions it is possible to assess the importance of different parameters contributing to ion specific behavior. We argue that the majority of specific ion effects involving relatively simple soft matter systems can be at least qualitatively understood and demystified.