Determination of van der Waals forces in monolayer films of lipids & biopolymers. Equation of state for two-dimensional films

Amphiphile molecules are characterized by the dual property arising from the interactions between the apolar [alkyl] and the polar part and the surrounding solvent, i.e., water. In assemblies which amphiphiles form in diverse systems, e.g., micelles, soap bubbles, monolayers or bilayers at interfaces, the attractive forces are attributed to the van der Waals forces. It is not easy to estimate the magnitude of van der Waals forces in some of these systems by any direct method.The magnitude of van der Waals forces in spread monolayers of lipids and biopolymers has been reported to be estimated from experimental data. The magnitude of these forces has been estimated by using an equation of state of a very general form, as delineated herein. In the current literature no such attempt has been reported in the analyses of these monolayers spread on aqueous surfaces. These analyses suggest that the predominant surface forces arise from van der Waals interactions, if the magnitude of electrostatic charge repulsions is weak. The equation-of-state as derived indicates that it is useful in providing information about the molecular interaction in monolayers, for both lipids and biopolymers.     

Forces controlling protein interactions: theory and experiment

This work reviews both the theory and experimental measurements of the fundamental forces that control protein solution behavior. In addition to the Derjaguin–Landau–Verwey–Overbeek (DLVO) forces, we also discuss the relative importance of hydrodynamic, solvation, and lock-and-key interactions in controlling protein solution behavior. The more common computational methods used to calculate both electrostatic and van der Waals potentials are described. Particular attention is given to the differences between proteins and ideal colloidal particles, and the computational methods used to address those differences. In addition to theoretical investigations of protein interactions, the results of recent direct measurements of the forces governing protein interactions are reviewed. These experimental results provide not only measurements against which the theories can be tested, but also demonstrate directly the relative importance of both DLVO and non-classical DLVO forces in the control of protein behavior.     

Critical capillary pressure for destruction of single foam films and foam: effect of foam film size

Foams and single foam films stabilised by ionic and amphiphile polymer surfactants are studied with foam pressure drop technique (FPDT) and thin liquid film-pressure balance technique (TLF-PBT). A pressure is reached at which the single foam films rupture and the foams destruct very fast (avalanche-like). For film rupture we named this pressure—critical capillary pressure of film rupture, P_cr,film while for foam destruction, we introduced a new parameter—critical capillary pressure of foam destruction, P_cr,foam. The surfactant kind and foam film type (common thin, common black and Newton black) affect the values of both parameters. When below 20 kPa, P_cr,film and P_cr,foam are close by value, when over 20 kPa, there is a significant difference between them. The P_cr,film versus film size and P_cr,foam versus foam dispersity dependences, indicate that the film size and foam dispersity strongly affects the critical capillary pressure values. Film size distribution histograms reveal that a foam always contains films that are of a larger than the most probable size. They rupture at lower pressures, does initiating the destruction of the whole foam, which can be an explanation why higher than 20 kPa there is a difference between P_cr,film and P_cr,foam values. This parameter, P_cr,foam is considered of significant with respect to foam stability and could find use in industry.     

The crystal and molecular structure of N-(17-methoxy-phenyl)-2-chloropyrrolo (2,3- b ) quinoline

N-(17-methoxy-phenyl)-2-chloropyrrolo (2,3-b) quinoline was solved by direct methods and refined to anR of 0.104 for 950 observed reflections. The intensity data were collected by the multiple film equi-inclination Weissenberg technique and estimated visually. The packing of the molecule is stabilised by van der Waals interaction. The pyrrolo (2,3-b) quinoline ring system is planar and the methoxy phenyl ring is approximately perpendicular to the plane of this ring system with a dihedral angle of 86.5°.     

Density functional theory augmented with an empirical dispersion term. Interaction energies and geometries of 80 noncovalent complexes compared with ab initio quantum mechanics calculations

Standard density functional theory (DFT) is augmented with a damped empirical dispersion term. The damping function is optimized on a small, well balanced set of 22 van der Waals (vdW) complexes and verified on a validation set of 58 vdW complexes. Both sets contain biologically relevant molecules such as nucleic acid bases. Results are in remarkable agreement with reference high-level wave function data based on the CCSD(T) method. The geometries obtained by full gradient optimization are in very good agreement with the best available theoretical reference. In terms of the standard deviation and average errors, results including the empirical dispersion term are clearly superior to all pure density functionals investigated-B-LYP, B3-LYP, PBE, TPSS, TPSSh, and BH-LYP-and even surpass the MP2/cc-pVTZ method. The combination of empirical dispersion with the TPSS functional performs remarkably well. The most critical part of the empirical dispersion approach is the damping function. The damping parameters should be optimized for each density functional/basis set combination separately. To keep the method simple, we optimized mainly a single factor, s(R), scaling globally the vdW radii. For good results, a basis set of at least triple-zeta quality is required and diffuse functions are recommended, since the basis set superposition error seriously deteriorates the results. On average, the dispersion contribution to the interaction energy missing in the DFT functionals examined here is about 15 and 100% for the hydrogen-bonded and stacked complexes considered, respectively.     

Direct Measurement of Repulsive van der Waals Interactions Using an Atomic Force Microscope

The forces of interaction between a flat poly(tetrafluoroethylene) (PTFE) surface and gold spheres (of radii 3–8 μm) were measured as a function of apparent surface separation for different intervening media. For air, fluorinated alkanes, and polar liquids the interaction between the surfaces was found to be attractive. With intervening liquids of low-polarity the interaction was found to be repulsive. This repulsion is attributed to a negative composite Hamaker coefficient leading to van der Waals repulsion.     

Surface forces in foam films from DPPC and lung surfactant phospholipid fraction

Surface properties of foam films formed from aqueous dispersions of dipalmitoyl-phosphatidylcholine (DPPC) and from solutions of a phospholipid fraction of lung surfactant (TPL) are studied employing the foam film method. Experiments are carried out within a wide range of NaCl concentrations (C_el) and the ranges of C_el determining formation of common films (CF), common black films (CBF) and bilayer Newton black films (NBF) are found. The thickness (h) of the CF and CBF decreases with the increase of C_el until the critical electrolyte concentrations (C_{el, cr}) is reached. The determined C_{el, cr} that characterize the transition to NBF show that C_{el, cr} of the TPL films is an order of magnitude higher than that of the DPPC films. The measured h of the TPL films is higher than that of the DPPC films in the whole C_el range. Besides, only the h(C_el) curve of the DPPC films outlines a metastable C_el range where both CF and NBF are obtained. Both the h(C_el) curves and the direct measurements of the disjoining pressure isotherms of the DPPC films (Π(h) isotherms) demonstrate the role of electrostatic repulsive forces for the stability of the phospholipid films The obtained results are compared with the DLVO theory equations and the evaluated potentials of the diffuse electric layer φ₀  20 mV for the DPPC films and φ₀  100 mV for TPL films show the strong effect of the charged phospholipids in the TPL mixture on the electric properties at the film interfaces.     

Influence of the type of foam films and the type of surfactant on foam stability

The behaviour and the life time ( _p) of different types of foam films (thin liquid films, for which DLVO-theory is valid; common black films, Newton black films) have been studied as a function of external pressure (P), applied in the Plateau-Gibbs-borders of the foam. The foam stability and the course of thep/P-dependence are determined mainly by the type of the foam films. A criterion for estimation of foam stability is proposed on the base of the obtained experimental results.     

Thinning of foam films of micellar surfactant solutions

Drainage in microscopic circular foam films depends significantly on the radial (tangential) mobility of the film surfaces and is accelerated as compared to the limiting case of tangentially immobile surfaces, where velocity of thinning is described by the classical Reynolds’ equation (outflow of viscous fluid from a cylindrical gap between two solid plates). The structure and composition of the adsorption layer and the interfacial mass transfer determine the tangential mobility of the film surfaces and, hence, the measured velocity of film thinning. Experiments with soluble surfactants below the critical micelle concentrations (CMC) have exhibited the effect of dynamic interfacial elasticity. At relatively low bulk concentrations, the interfacial mass transfer is governed by surface diffusion; close to CMC (saturated adsorption layer), the limiting case of tangentially immobile surfaces can be reached and at concentrations above the CMC the film thinning is accelerated again. Here, we report freshly established data on the kinetic behavior of foam films from micellar solutions of soluble nonionic surfactants (decyl-octaoxyethylene alcohol and dodecyl-octaoxyethylene alcohol) in a wide range of concentrations above the CMC aiming to investigate the effect of partially disintegrated micelles acting as sources of surfactant molecules at the surface.     

Long-Range van der Waals Interactions in Density Functional Theory

The early difficulties in accounting for long-range van der Waals interactions in the framework of density functional theory (DFT) have been overcome to a certain extent in recent works by several groups, and those interactions can be computed numerically. In this paper a derivation of the analytical form of the attractive van der Waals interaction between two neutral atoms with polarizabilities α₁ and α₂ at large distance R, namely E _int=−C ₆ α₁ α₂/R ⁶ is performed within the context of DFT. Use is made of the properties of the Coulomb correlation hole, and it is shown that nonlocal Coulomb correlations are responsible for long-range dispersion interactions.     

分子间作用力对咪唑盐介晶相性质的影响

通过对咪唑环1位(N1)取代烷基、3位(N3)取代基及阴离子的修饰合成了一系列具有近晶A (SmA)相的咪唑类离子液晶. 利用差示扫描量热法、单晶衍射、小角度X射线衍射等手段研究了咪唑盐的介晶相温度范围、介晶态的结构, 并测量了部分咪唑盐的各向异性导电率. 结果表明, 咪唑环N1取代烷基、N3取代基及咪唑盐的阴离子会改变分子间范德华力和氢键, 从而对咪唑盐的介晶相性质产生影响. 此外, 当乙烯基引入到咪唑环N3位置时, 咪唑盐相邻的层结构之间形成π-π堆积作用, 不仅有利于介晶态的形成, 同时使氟硼酸类离子液晶具有最大的层间距和最小的各向异性导电率. 这一结果表明, 调控离子液晶的性质时必须综合考虑各种分子间作用力的影响.     

Dative N→P/Si Interactions — A Historical Approach [1]

The dative N→Si/P interactions in 8‐dimethylamino‐naphth‐1‐yl‐silanes and phosphorus compounds are largely an artefact which originated from insufficient perusal of the pertinent literature.     

Calculation of van der Waals interactions involving lipid vesicles

Van der Waals energies of interaction involving vesicles and lipid layers are calculated for different geometries. Results from exact and approximate calculations are compared with some existing experimental data. It is shown that sufficient accuracy can be obtained using relatively simple ‘additivity’ approximations for the contribution of dispersion interactions. A set of calculated results is presented for a small unilamellar vesicle interacting with coated and uncoated metal and polymer surfaces. A lipid coating lowers magnitude of the interaction energy approximately two-fold. The procedure gives a simple possibility to estimate Hamaker constants (and ‘Hamaker functions’) from handbook data taking into account the existing uncertainity in the materials constants of the interacting substances.     

Accurate description of van der Waals complexes by density functional theory including empirical corrections

An empirical method to account for van der Waals interactions in practical calculations with the density functional theory (termed DFT-D) is tested for a wide variety of molecular complexes. As in previous schemes, the dispersive energy is described by damped interatomic potentials of the form C6R(-6). The use of pure, gradient-corrected density functionals (BLYP and PBE), together with the resolution-of-the-identity (RI) approximation for the Coulomb operator, allows very efficient computations for large systems. Opposed to previous work, extended AO basis sets of polarized TZV or QZV quality are employed, which reduces the basis set superposition error to a negligible extend. By using a global scaling factor for the atomic C6 coefficients, the functional dependence of the results could be strongly reduced. The "double counting" of correlation effects for strongly bound complexes is found to be insignificant if steep damping functions are employed. The method is applied to a total of 29 complexes of atoms and small molecules (Ne, CH4, NH3, H2O, CH3F, N2, F2, formic acid, ethene, and ethine) with each other and with benzene, to benzene, naphthalene, pyrene, and coronene dimers, the naphthalene trimer, coronene. H2O and four H-bonded and stacked DNA base pairs (AT and GC). In almost all cases, very good agreement with reliable theoretical or experimental results for binding energies and intermolecular distances is obtained. For stacked aromatic systems and the important base pairs, the DFT-D-BLYP model seems to be even superior to standard MP2 treatments that systematically overbind. The good results obtained suggest the approach as a practical tool to describe the properties of many important van der Waals systems in chemistry. Furthermore, the DFT-D data may either be used to calibrate much simpler (e.g., force-field) potentials or the optimized structures can be used as input for more accurate ab initio calculations of the interaction energies.     

X-ray crystallographic studies and molecular calculations on 1∶1 inclusion complexes of cholic acid with acetophenone and its derivatives

Molecular calculations were applied to four channel-type inclusion complexes of cholic acid (CA) with acetophenone or its derivatives (3-, 4-fluoroacetophenone and 2-chloroacetophenone). According to the calculated results, both the total and van der Waals interaction energies between channel and included guests depend on the channel form determined by the guest species. Similarly, the channel form is responsible for the dipole moment of the channel. Further examination of the results suggests that dipole-dipole interaction does not play an important role in the determination of the guest orientation. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82193 (26 pages).     

Alkane films on water: stability and wetting transitions

Types of surface forces determining the disjoining pressure isotherms of wetting films of low-molecular-weight alkanes on water surface are discussed. The van der Waals forces in alkane interlayers at different temperatures were calculated using a combination of exact equations of the Dzyaloshinsky—Lifshitz—Pitaevsky macroscopic theory and the multi-oscillator model for representation of the dielectric permittivity spectra of contacting bodies. Taking account of competitive action of the van der Waals and image forces allows one not only to reproduce specific features of wetting in the systems studied at different temperatures, but also to describe quantitatively the contact angles and the experimentally observed isotherms of polymolecular adsorption. The experimentally detected wetting transition in the water—pentane—vapor system was rationalized using the results of calculations mentioned above and the Derjaguin—Frumkin theory of wetting. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 256–266, February, 2008.     

Intermolecular Interactions and the Adhesion of Oleic Acid

The method presented by Good, van Oss, and Chaudhury was applied to characterize intermolecular interactions and the adhesion of oleic acid to selected model surfaces. Interfacial tensions of oleic acid were on the order 11–12 mJ/m² in aqueous solutions and 31–32 mJ/m² at air. The dispersive contribution to the surface tension of oleic acid against different neutral interfaces was determined to be 24–31 mJ/m² in air. Contact angles of oleic acid on selected hydrophilic and hydrophobic model surfaces were measured both in air and in aqueous solution. Van der Waals (dispersive) interactions determined the wetting properties of oleic acid in air both on nonpolar and basic surfaces. As expected, the adhesion of oleic acid to hydrophilic surfaces was much lower and to hydrophobic surfaces higher in aqueous environment than in air. The adhesion in aqueous environment is mainly governed by the cohesive and adhesive properties of water. It was concluded that the GvOC method in this case was only capable to give qualitative information about Lewis acid-base and van der Waals properties of surfaces and liquids, an important limiting factor being the asymmetry of oleic acid and the common probe liquids (diiodomethane and water).