Advances in Colloid and Interface Science (v.208, #C)

Honorary note for Wolfgang Helfrich by Dieter Vollhardt (vii-ix).

Orthoconic liquid crystals — A case study by Sven T. Lagerwall (1-9).
Since the early investigations on liquid crystals it was realized how the confining surfaces often determine the textures and even properties of the material. This influence is particularly complex and important for chiral materials. When we come to chiral smectics the surfaces may have dramatic effects. These are illustrated on the ferroelectric liquid crystals; they then again increase in importance for the antiferroelectric liquid crystals where the most recent example is given by the orthoconic liquid crystals.Display Omitted
Keywords: Chiral liquid crystals; Ferroelectric liquid crystals; Antiferroelectric liquid crystals; Orthoconic liquid crystals; Orthoconic condition; Synclinic structure; Anticlinic structure; Dielectric tensor; Surface alignment; Surface stabilization; Displays;

In 1978 Wolfgang Helfrich published a paper (Helfrich W. Z Naturforsch 1978; 33a:305) where he introduced the notion of an undulation force between bilayers. This is caused by thermal excitations of the bending modes being restricted by the presence of neighboring layers. Although there is now a consensus on the qualitative picture put forward by Helfrich there is still a debate concerning the quantitative aspects. We discuss in particular the distance dependence of the interaction and also the value of the numerical coefficient of the force law derived by Helfrich.Display Omitted
Keywords: Fluid membranes;

Biomimetic membranes are fluid and can undergo two different elastic deformations, bending and stretching. The bending of a membrane is primarily governed by two elastic parameters: its spontaneous (or preferred) curvature m and its bending rigidity κ. These two parameters define an intrinsic tension scale, the spontaneous tension 2  κm 2. Membrane stretching and compression, on the other hand, are determined by the mechanical tension acting within the membrane. For vesicle membranes, the two elastic deformations are coupled via the enclosed vesicle volume even in the absence of mechanical forces as shown here by minimizing the combined bending and stretching energy with respect to membrane area for fixed vesicle volume. As a consequence, the mechanical tension within a vesicle membrane depends on the spontaneous curvature and on the bending rigidity. This interdependence, which is difficult to grasp intuitively, is then illustrated for a variety of simple vesicle shapes. Depending on the vesicle morphology, the magnitude of the mechanical tension can be comparable to or can be much smaller than the spontaneous tension.Display Omitted
Keywords: Membranes and vesicles; Curvature elasticity; Spontaneous curvature; Compressible membranes; Mechanical tension;

Helfrich model of membrane bending: From Gibbs theory of liquid interfaces to membranes as thick anisotropic elastic layers by Felix Campelo; Clement Arnarez; Siewert J. Marrink; Michael M. Kozlov (25-33).
Helfrich model of membrane bending elasticity has been most influential in establishment and development of Soft-Matter Physics of lipid bilayers and biological membranes. Recently, Helfrich theory has been extensively used in Cell Biology to understand the phenomena of shaping, fusion and fission of cellular membranes. The general background of Helfrich theory on the one hand, and the ways of specifying the model parameters on the other, are important for quantitative treatment of particular biologically relevant membrane phenomena. Here we present the origin of Helfrich model within the context of the general Gibbs theory of capillary interfaces, and review the strategies of computing the membrane elastic moduli based on considering a lipid monolayer as a three-dimensional thick layer characterized by trans-monolayer profiles of elastic parameters. We present the results of original computations of these profiles by a state-of-the-art numerical approach.Display Omitted
Keywords: Membrane elasticity; Surface thermodynamics; Curvature; Trans-monolayer elasticity profile; Molecular dynamics;

Physical aspects of heterogeneities in multi-component lipid membranes by Shigeyuki Komura; David Andelman (34-46).
Ever since the raft model for biomembranes has been proposed, the traditional view of biomembranes based on the fluid-mosaic model has been altered. In the raft model, dynamical heterogeneities in multi-component lipid bilayers play an essential role. Focusing on the lateral phase separation of biomembranes and vesicles, we review some of the most relevant research conducted over the last decade. We mainly refer to those experimental works that are based on physical chemistry approach, and to theoretical explanations given in terms of soft matter physics. In the first part, we describe the phase behavior and the conformation of multi-component lipid bilayers. After formulating the hydrodynamics of fluid membranes in the presence of the surrounding solvent, we discuss the domain growth-law and decay rate of concentration fluctuations. Finally, we review several attempts to describe membrane rafts as two-dimensional microemulsion.Display Omitted
Keywords: Lipid membranes; Membrane rafts; Domains in membranes; Phase separation in membranes; Lipid cholesterol; Mixtures; Hydrodynamics of fluid membranes; Saffman–Delbruck model;

Bending lipid membranes: Experiments after W. Helfrich's model by Patricia Bassereau; Benoit Sorre; Aurore Lévy (47-57).
Current description of biomembrane mechanics originates for a large part from W. Helfrich's model. Based on his continuum theory, many experiments have been performed in the past four decades on simplified membranes in order to characterize the mechanical properties of lipid membranes and the contribution of polymers or proteins. The long-term goal was to develop a better understanding of the mechanical properties of cell membranes. In this paper, we will review representative experimental approaches that were developed during this period and the main results that were obtained.Display Omitted
Keywords: Membrane bending; Spontaneous curvature; Membrane mechanics; Model membrane;

Line active molecules promote inhomogeneous structures in membranes: Theory, simulations and experiments by Benoit Palmieri; Tetsuya Yamamoto; Robert C. Brewster; Samuel A. Safran (58-65).
We review recent theoretical efforts that predict how line-active molecules can promote lateral heterogeneities (or domains) in model membranes. This fundamental understanding may be relevant to membrane composition in living cells, where it is thought that small domains, called lipid rafts, are necessary for the cells to be functional. The theoretical work reviewed here ranges in scale from coarse grained continuum models to nearly atomistic models. The effect of line active molecules on domain sizes and shapes in the phase separated regime or on fluctuation length scales and lifetimes in the single phase, mixed regime, of the membrane is discussed. Recent experimental studies on model membranes that include line active molecules are also presented together with some comparisons with the theoretical predictions.Display Omitted
Keywords: Linactants; Model membranes; Nanodomains; Lipid rafts;

Recent theoretical advances in elasticity of membranes following Helfrich's famous spontaneous curvature model are summarized in this review. The governing equations describing equilibrium configurations of lipid vesicles, lipid membranes with free edges, and chiral lipid membranes are presented. Several analytic solutions to these equations and their corresponding configurations are demonstrated.Display Omitted
Keywords: Helfrich's spontaneous curvature model; Elasticity of membrane; Governing equation; Analytic solution;

Dynamics and instabilities of lipid bilayer membrane shapes by Zheng Shi; Tobias Baumgart (76-88).
Biological membranes undergo constant shape remodeling involving the formation of highly curved structures. The lipid bilayer represents the fundamental architecture of the cellular membrane with its shapes determined by the Helfrich curvature bending energy. However, the dynamics of bilayer shape transitions, especially their modulation by membrane proteins, and the resulting shape instabilities, are still not well understood. Here, we review in a unifying manner several theories that describe the fluctuations (i.e. undulations) of bilayer shapes as well as their local coupling with lipid or protein density variation. The coupling between local membrane curvature and lipid density gives rise to a ‘slipping mode’ in addition to the conventional ‘bending mode’ for damping the membrane fluctuation. This leads to a number of interesting experimental phenomena regarding bilayer shape dynamics. More importantly, curvature-inducing proteins can couple with membrane shape and eventually render the membrane unstable. A criterion for membrane shape instability is derived from a linear stability analysis. The instability criterion reemphasizes the importance of membrane tension in regulating the stability and dynamics of membrane geometry. Recent progresses in understanding the role of membrane tension in regulating dynamical cellular processes are also reviewed. Protein density is emphasized as a key factor in regulating membrane shape transitions: a threshold density of curvature coupling proteins is required for inducing membrane morphology transitions.Display Omitted
Keywords: Membrane fluctuation; Interleaflet friction; Membrane tension; Curvature instability; Protein density; Membrane shape transition;

Fluid lipid membranes can mediate forces between particles bound to them: A local deformation of the surface geometry created by some object spreads to distant regions, where other objects can respond to it. The physical characteristics of these geometric interactions, and how they are affected by thermal fluctuations, are well described by the simple continuum curvature-elastic Hamiltonian proposed 40 years ago by Wolfgang Helfrich. Unfortunately, while the underlying principles are conceptually straightforward, the corresponding calculations are not—largely because one must enforce boundary conditions for finite-sized objects. This challenge has inspired several heuristic approaches for expressing the problem in a point particle language. While streamlining the calculations of leading order results and enabling predictions for higher order corrections, the ad hoc nature of the reformulation leaves its domain of validity unclear. In contrast, the framework of Effective Field Theory (EFT) provides a systematic way to construct a completely equivalent point particle description. In this review we present a detailed account for how this is accomplished. In particular, we use a familiar example from electrostatics as an analogy to motivate the key steps needed to construct an EFT, most notably capturing finite size information in point-like “polarizabilities,” and determining their value through a suitable “matching procedure.” The interaction (free) energy then emerges as a systematic cumulant expansion, for which powerful diagrammatic techniques exist, which we also briefly revisit. We then apply this formalism to derive series expansions for interactions between flat and curved particle pairs, multibody interactions, as well as corrections to all these interactions due to thermal fluctuations.Display Omitted
Keywords: Lipid membranes; Proteins; Mediated interactions; Effective Field Theory;

Bilayers and monolayers are excellent models of biological membranes. The constituents of the biological membranes such as lipids, cholesterols and proteins are chiral. Chiral molecules are abundant in nature (protein, nucleic acid and lipid). It is obvious that relationship between chirality and morphology (as well as function) of biological membrane is of interest for its fundamental importance and has technological implication regarding various membrane functions. The recent years have witnessed that a number of experimental studies in biomimetic systems have shown fascinating morphologies where chirality of the constituent molecule has decisive influence. Significant progress is made towards the understanding of these systems from the theoretical and computational studies. Helfrich's concept of intrinsic force arising from chirality is a milestone in understanding the biomimetic system such as bilayer and the related concepts, further progresses in molecular understanding made in recent years and experimental studies revealing the influence of chirality on morphology are the focus of the present review. Helfrich's concept of intrinsic force arising due to chirality is useful in understanding two-dimensional bilayers and one-dimensional monolayers and related mimetic systems. Various experimental techniques are used, which can probe the molecular architecture of these mimetic systems at different length scales and both macroscopic (thermodynamic) as well as microscopic (molecular) theories are developed. These studies are aimed to understand the role of chirality in the molecular interaction when the corresponding molecule is present in an aggregate. When one looks into the variety of morphologies exhibited by three-dimensional bilayer and two-dimensional monolayer, the later types of systems are more exotic in the sense that they show more diversity and interesting chiral discrimination. Helfrich's concept of intrinsic force may be considered useful in both cases. The intrinsic force due to chirality is the decisive factor in determining morphology which is explained by molecular approaches. Finally, biological and technological implications of such morphological variations are briefly mentioned.Display Omitted
Keywords: Intrinsic force; Chirality; Monolayer; Bilayer; Membrane;

About 40 years ago, Helfrich introduced an elastic model to explain shapes and shape transitions of cells (Z Naturforsch C, 1973; 28:693). This seminal article stimulated numerous theoretical as well as experimental investigations and created new research fields. In particular, the predictive power of his approach was demonstrated in a large variety of lipid model system. Here in this review, we focus on the development with respect to planar lipid membranes in external electric fields. Stimulated by the early work of Helfrich on electric field forces acting on liposomes, we extended his early approach to understand the kinetics of lipid membrane rupture. First, we revisit the main forces determining the kinetics of membrane rupture followed by an overview on various experiments. Knowledge on the kinetics of defect formation may help to design stable membranes or serve for novel mechanism for controlled release.Display Omitted
Keywords: Lipid membrane; Elastic model; Rupture; Electric field; Pores; Lipid pores;

Fluid vesicles in flow by David Abreu; Michael Levant; Victor Steinberg; Udo Seifert (129-141).
We review the dynamical behavior of giant fluid vesicles in various types of external hydrodynamic flow. The interplay between stresses arising from membrane elasticity, hydrodynamic flows, and the ever present thermal fluctuations leads to a rich phenomenology. In linear flows with both rotational and elongational components, the properties of the tank-treading and tumbling motions are now well described by theoretical and numerical models. At the transition between these two regimes, strong shape deformations and amplification of thermal fluctuations generate a new regime called trembling. In this regime, the vesicle orientation oscillates quasi-periodically around the flow direction while asymmetric deformations occur. For strong enough flows, small-wavelength deformations like wrinkles are observed, similar to what happens in a suddenly reversed elongational flow. In steady elongational flow, vesicles with large excess areas deform into dumbbells at large flow rates and pearling occurs for even stronger flows. In capillary flows with parabolic flow profile, single vesicles migrate towards the center of the channel, where they adopt symmetric shapes, for two reasons. First, walls exert a hydrodynamic lift force which pushes them away. Second, shear stresses are minimal at the tip of the flow. However, symmetry is broken for vesicles with large excess areas, which flow off-center and deform asymmetrically. In suspensions, hydrodynamic interactions between vesicles add up to these two effects, making it challenging to deduce rheological properties from the dynamics of individual vesicles. Further investigations of vesicles and similar objects and their suspensions in steady or time-dependent flow will shed light on phenomena such as blood flow.Display Omitted
Keywords: Vesicle; Viscous flow; Bending energy; Thermal fluctuations; Migration; Rheology;

Hydration repulsion between membranes and polar surfaces: Simulation approaches versus continuum theories by Matej Kanduč; Alexander Schlaich; Emanuel Schneck; Roland R. Netz (142-152).
A review of various computer simulation approaches for the study of the hydration repulsion between lipid membranes and polar surfaces is presented. We discuss different methods and compare their advantages and limitations. We consider interaction pressures, interaction thermodynamics, and interaction mechanisms. We take a close look at the influence of the experimental boundary conditions and at repulsion mechanisms due to the unfavorable overlap of interfacial water layers. To this end, we analyze several distinct water order parameters in simulations of interacting polar surfaces and compare the results to the predictions of simple continuum theories.Display Omitted
Keywords: Hydration repulsion; Biological membranes; Phospholipids; MD simulations; Landau theory; Order parameters;

The endoplasmatic reticulum (ER) comprises flattened vesicles (cisternae) with worm holes dubbed with ribosomes coexisting with a network of interconnected tubes which can extend to the cell periphery or even penetrate nerve axons. The coexisting topologies enclose a continuous luminal space. The complex ER topology is specifically controlled by a group of ER-shaping proteins often called reticulons (discovered by the group of Tom Rapoport [1]). They include atlastin, reticulon, REEP and the MT severing protein spastin. A generic ER shape controlling factor is the necessity to maximize the area-to-volume ratio of ER membranes in the highly crowded cytoplasmic space. I present a model of the ER-shaping function of the reticulons based on the Helfrich bending elasticity concept of soft shell shape changes. Common structural motifs of the reticulons are hydrophobic sequences forming wedge shaped hairpins which penetrate the lipid bilayer of the cell membranes. The wedge-like hydrophobic anchors can both induce the high curvature of the tubular ER fraction and ensure the preferred distribution of the reticulons along the tubules. Tubular junctions may be stabilized by the reticulons forming two forceps twisted by 90°. The ER extensions to the cell periphery and the axons are mediated by coupling of the tubes to the microtubules which is mediated by REEP and spastin. At the end I present a model of the tension driven homotype fusion of ER-membranes by atlastin, based on analogies to the SNARE–complexin–SNARE driven heterotype fusion process.Endoplasmatic reticulum membranes can form extended networks of interconnected tubules (shown on the top) similar to micro-emulsions (shown at the bottom). We describe the physical basis of the formation and stabilization of these extended membrane system by ER-shaping proteins of the reticulon super-family and a generic mechanism maximizing the area-to-volume ratio in the crowded intracellular space.Display Omitted
Keywords: Curvature elasticity concept of biomembrane functions; Endoplasmatic reticulum shaping proteins; Membrane fusion; Membrane microtubule coupling; Lipid protein interaction; Reticulons; Atlastin; Spastin;

Hydrodynamic lift forces acting on cells and particles in fluid flow receive ongoing attention from medicine, mathematics, physics and engineering. The early findings of Fåhræus & Lindqvist on the viscosity change of blood with the diameter of capillaries motivated extensive studies both experimentally and theoretically to illuminate the underlying physics. We review this historical development that led to the discovery of the inertial and non-inertial lift forces and elucidate the origins of these forces that are still not entirely clear. Exploiting microfluidic techniques induced a tremendous amount of new insights especially into the more complex interactions between the flow field and deformable objects like vesicles or red blood cells. We trace the way from the investigation of single cell dynamics to the recent developments of microfluidic techniques for particle and cell sorting using hydrodynamic forces. Such continuous and label-free on-chip cell sorting devices promise to revolutionize medical analyses for personalized point-of-care diagnosis. We present the state-of-the-art of different hydrodynamic lift-based techniques and discuss their advantages and limitations.Display Omitted
Keywords: Microfluidics; Hydrodynamic lift; Vesicles; Red blood cells; Lab on a chip; Cell sorting and separation;

Counterion-mediated pattern formation in membranes containing anionic lipids by David R. Slochower; Yu-Hsiu Wang; Richard W. Tourdot; Ravi Radhakrishnan; Paul A. Janmey (177-188).
Most lipid components of cell membranes are either neutral, like cholesterol, or zwitterionic, like phosphatidylcholine and sphingomyelin. Very few lipids, such as sphingosine, are cationic at physiological pH. These generally interact only transiently with the lipid bilayer, and their synthetic analogs are often designed to destabilize the membrane for drug or DNA delivery. However, anionic lipids are common in both eukaryotic and prokaryotic cell membranes. The net charge per anionic phospholipid ranges from − 1 for the most abundant anionic lipids such as phosphatidylserine, to near − 7 for phosphatidylinositol 3,4,5 trisphosphate, although the effective charge depends on many environmental factors. Anionic phospholipids and other negatively charged lipids such as lipopolysaccharides are not randomly distributed in the lipid bilayer, but are highly restricted to specific leaflets of the bilayer and to regions near transmembrane proteins or other organized structures within the plane of the membrane. This review highlights some recent evidence that counterions, in the form of monovalent or divalent metal ions, polyamines, or cationic protein domains, have a large influence on the lateral distribution of anionic lipids within the membrane, and that lateral demixing of anionic lipids has effects on membrane curvature and protein function that are important for biological control.Display Omitted
Keywords: Anionic phospholipids; Divalent counterions; Membrane patterning;

About forty years ago it was realized that phospholipid membranes, because they are composed of two layers, exhibit particular, and specific mechanical properties [1–3]. This led to the concept of nonlocal membrane bending, often called area difference elasticity. We present a short history of the development of the concept, followed by arguments for a proper definition of the corresponding elastic constant. The effects of the nonlocal bending energy on vesicle shape are explained. It is demonstrated that lipid vesicles, cells and cellular aggregates exhibit phenomena that can only be described in a complete manner by considering nonlocal bending.
Keywords: Lamellar membranes; Area difference elasticity; Vesicle shape; Membrane tethers; Flip-flop; Vesicle fusion; Monocellular sheets;

Langmuir monolayers as models to study processes at membrane surfaces by Cristina Stefaniu; Gerald Brezesinski; Helmuth Möhwald (197-213).
The use of new sophisticated and highly surface sensitive techniques as synchrotron based X-ray scattering techniques and in-house infrared reflection absorption spectroscopy (IRRAS) has revolutionized the monolayer research. Not only the determination of monolayer structures but also interactions between amphiphilic monolayers at the soft air/liquid interface and molecules dissolved in the subphase are important for many areas in material and life sciences. Monolayers are convenient quasi-two-dimensional model systems. This review focuses on interactions between amphiphilic molecules in binary and ternary mixtures as well as on interfacial interactions with interesting biomolecules dissolved in the subphase. The phase state of monolayers can be easily triggered at constant temperature by increasing the packing density of the lipids by compression. Simultaneously the monolayer structure changes are followed in situ by grazing incidence X-ray diffraction or IRRAS. The interactions can be indirectly determined by the observed structure changes. Additionally, the yield of enzymatic reaction can be quantitatively determined, secondary structures of peptides and proteins can be measured and compared with those observed in bulk. In this way, the influence of a confinement on the structural properties of biomolecules can be determined. The adsorption of DNA can be quantified as well as the competing adsorption of ions at charged interfaces. The influence of modified nanoparticles on model membranes can be clearly determined. In this review, the relevance and utility of Langmuir monolayers as suitable models to study physical and chemical interactions at membrane surfaces are clearly demonstrated.Display Omitted
Keywords: Monolayers; Bilayers; GIXD; IRRAS; Interactions; Lipids; DNA; Peptides; Nanoparticles; Interfacial reactions;

Wrapping of nanoparticles by membranes by Amir H. Bahrami; Michael Raatz; Jaime Agudo-Canalejo; Raphael Michel; Emily M. Curtis; Carol K. Hall; Michael Gradzielski; Reinhard Lipowsky; Thomas R. Weikl (214-224).
How nanoparticles interact with biomembranes is central for understanding their bioactivity. Biomembranes wrap around nanoparticles if the adhesive interaction between the nanoparticles and membranes is sufficiently strong to compensate for the cost of membrane bending. In this article, we review recent results from theory and simulations that provide new insights on the interplay of bending and adhesion energies during the wrapping of nanoparticles by membranes. These results indicate that the interplay of bending and adhesion during wrapping is strongly affected by the interaction range of the particle–membrane adhesion potential, by the shape of the nanoparticles, and by shape changes of membrane vesicles during wrapping. The interaction range of the particle–membrane adhesion potential is crucial both for the wrapping process of single nanoparticles and the cooperative wrapping of nanoparticles by membrane tubules.Display Omitted
Keywords: Nanoparticles; Membranes; Bending energy;

This review gives a brief overview of experimental approaches used to assess the bending rigidity of membranes. Emphasis is placed on techniques based on the use of giant unilamellar vesicles. We summarize the effect on the bending rigidity of membranes as a function of membrane composition, presence of various inclusions in the bilayer and molecules and ions in the bathing solutions. Examples for the impact of temperature, cholesterol, some peptides and proteins, sugars and salts are provided and the literature data are discussed critically. Future directions, open questions and possible developments in this research field are also included.Display Omitted
Keywords: Bending rigidity; Giant vesicles; Fluctuation spectroscopy; Micropipette aspiration; Vesicle electrodeformation; Cholesterol;

Lipophilic nucleic acids — A flexible construction kit for organization and functionalization of surfaces by Matthias Schade; Debora Berti; Daniel Huster; Andreas Herrmann; Anna Arbuzova (235-251).
Lipophilic nucleic acids have become a versatile tool for structuring and functionalization of lipid bilayers and biological membranes as well as cargo vehicles to transport and deliver bioactive compounds, like interference RNA, into cells by taking advantage of reversible hybridization with complementary strands. This contribution reviews the different types of conjugates of lipophilic nucleic acids, and their physicochemical and self-assembly properties. Strategies for choosing a nucleic acid, lipophilic modification, and linker are discussed. Interaction with lipid membranes and its stability, dynamic structure and assembly of lipophilic nucleic acids upon embedding into biological membranes are specific points of the review. A large diversity of conjugates including lipophilic peptide nucleic acid and siRNA provides tailored solutions for specific applications in bio- and nanotechnology as well as in cell biology and medicine, as illustrated through some selected examples.Display Omitted
Keywords: Lipophilic nucleotides; Self-assembly; DNA; Liposomes; Membranes; Cells;

Hydrogels from phospholipid vesicles by D. Gräbner; H. Hoffmann; S. Förster; S. Rosenfeldt; J. Linders; C. Mayer; Y. Talmon; J. Schmidt (252-263).
It is shown that phospholipid dispersions with a few percent of diacylphosphocholine PC in water can be swollen to single-phase lyotropic liquid crystalline Lα-phases by the addition of co-solvents like glycerol, 1,3-butyleneglycol BG or 1,2-propyleneglycol PG. The birefringent Lα-phases contain small unilamellar and multilamellar vesicles if the temperature of the samples is above the Krafft-Temperature Tm of the phospholipid. When such transparent birefringent viscous samples are cooled down below Tm the samples are transformed into birefringent gels. Cryo-TEM and FF-TEM measurements show that the bilayers of the vesicles are transformed from the liquid to the crystalline state during the transformation while the vesicle structure remains. The bilayers of the crystalline vesicles form adhesive contacts in the gel. Pulsed-field gradient NMR measurements show that two different kinds of water or co-solvent can be distinguished in the gels. One type of solvent molecules can diffuse like normal solvent in a continuous bulk phase. A second type of water diffuses much more slowly. This type of solvent is obviously trapped in the vesicles. The permeability of the crystalline vesicles for water and solvent molecules is much lower in the crystalline state than in the fluid state.Maximum swelling of the diacylphosphocholin dispersions occurs when the refractive index of the solvent is matched to the refractive index of the bilayers. The attraction between the bilayers is at a minimum in this state and the liquid crystalline Lα-phase's undulation forces between the bilayers push the bilayers apart. On transformation to the gel state the crystalline bilayers assume a high elastic bending rigidity. Undulations of the bilayers are now suppressed, and the bilayers can form adhesive contacts.Oscillating rheological measurements show that the gels with only 1% of phospholipids can have a storage modulus of 1000 Pa. The gels are very brittle. They break when they are deformed by a few percent.Cryo-TEM micrograph of multilamellar vesicles with crystalline bilayers.Display Omitted
Keywords: Diacylphosphocholin; Vesicles; Gels; Swelling of dispersions;

Self-assembly of different single-chain bolaphospholipids and their miscibility with phospholipids or classical amphiphiles by Alfred Blume; Simon Drescher; Gesche Graf; Karen Köhler; Annette Meister (264-278).
A variety of bolalipids with a single long alkyl chain and two identical headgroups self-assemble in aqueous solutions into helical entangled nanofibers leading to the formation of a hydrogel. An increase in temperature usually leads to the break-up of the fiber structure into micellar aggregates. In this paper the question is addressed whether bolalipids of different lengths or different headgroup structures can form mixed fibers. Also, the stability of the fiber aggregation of bolalipids in mixtures with phospholipids forming lamellar bilayers is discussed. Here, the question whether single-chain bolalipids can be incorporated into phospholipid bilayers to stabilize bilayer membranes is important, as possibly lipid vesicles used for drug delivery can be improved. Finally, the stability of the fiber aggregate against solubilisation by common surfactants was studied. The paper addresses the question which type of aggregate structure dominates the self-assembly of bipolar and monopolar amphiphiles in aqueous suspension.Display Omitted
Keywords: Bolalipids; Phospholipids; Surfactants; Self-assembly; Miscibility; Aggregation behavior; Nanofibers; Bilayers; Micelles;

The self-assembly of amphiphilic molecules into fibrous structures has been the subject of numerous studies over past decades due to various current and promising technical applications. Although very different in their head group chemistry many natural as well as synthetic amphiphilic compounds derived from carbohydrates, carbocyanine dyes, or amino acids tend to form fibrous structures by molecular self-assembly in water predominantly twisted ribbons or tubes. Often a transition between these assembly structures is observed, which is a phenomenon already theoretically approached by Wolfgang Helfrich and still focus point in current research. With the development of suitable sample preparation and electron optical imaging techniques, cryogenic transmission electron microscopy (cryo-TEM) in combination with three-dimensional (3D) reconstruction techniques has become a particular popular direct characterization technique for supramolecular assemblies in general. Here we review the recent progress in deriving precise structural information from cryo-TEM data of particularly fibrous structures preferably in three dimensions.Display Omitted
Keywords: Ribbon; Tube; Chirality; Cryogenic transmission electron microscopy; 3D reconstruction; Cryo-electron tomography;