Lattice and thermodynamic characteristics of N-stearoyl-allo-threonine monolayers

The effect of the second chiral center of diastereomeric N-alkanoyl-allo-threonine on the main monolayer characteristics has been investigated. The characteristic features of the enantiomeric and racemic forms of N-stearoyl-allo-threonine monolayers are studied on a thermodynamic basis and molecular scale. The π–A curves of the enantiomeric and racemic allo-forms show similar features to those of N-stearoyl-threonine. The compression curves are always located above the corresponding decompression curves and the decompression curves can be used as equilibrium isotherms for both the enantiomeric and racemic N-stearoyl-allo-threonine. The absolute T0-values (disappearance of the LE/LC-transition) are 4–5 K larger compared with the corresponding N-stearoyl-threonines,} but the ΔT0 between the enantiomeric (d) and the racemic (dl) forms is only slightly larger than that of N-stearoyl-threonine. The difference in the critical temperatures Tc{,} above which the monolayer cannot be compressed into the condensed state{,} between the enantiomeric and the racemic forms{,} is quite small (ΔTc = 0.8 K) and is smaller compared to that of the corresponding threonines (ΔTc = 1.8 K). This is consistent with the dominance of the van der Waals interactions between the alkyl chains reducing the influence of chirality on the thermodynamic parameters. GIXD studies of N-stearoyl-allo-threonine monolayers provide information about the lattice structure of condensed monolayer phases on the Angstrom scale and stipulate the homochiral or heterochiral preference in the condensed phases. Comparable to N-stearoyl-threonine{,} the enantiomers exhibit an oblique lattice structure{,} whereas the racemates form a NNN tilted orthorhombic structure demonstrating the dominance of heterochiral interactions in the racemates independent of the diasteomeric structure change of the polar head group. The A0 values are characteristic for rotator phases. The smaller A0 value obtained for the racemic monolayers indicates their tighter packing caused by heterochiral interactions. The program Hardpack was used to predict the geometric parameters of possible 2-dimensional packings. For comparison with the experimental GIXD data{, the two-dimensional lattice parameters and characteristic features of the enantiomeric and racemic diastereomeric stearoyl-threonine monolayers were calculated and are in reasonable agreement with the experimental GIXD data

Phase behavior of selected artificial lipids

The flexibility of biomembranes is based on the physical-chemical properties of their main components - glycerophospholipids. The structure of these modular amphiphilic molecules can be modified through organic synthesis making it possible to study specific physical-chemical effects in detail. In particular, the roles of the hydrophobic tails of the phospholipids and their hydrophobic/hydrophilic interfacial backbone on the phase behaviour are highlighted. The spatial orientation of the glycerol backbone changes from sn-1,2 to sn-1,3 phospholipids leading to an increase of the in-plane area of the molecule. The larger distance between the hydrophobic tails can lead to membrane leaflet interdigitation. The introduction of methyl side groups in the hydrophobic tails increases the fluidity of the bilayer. Depending on the position of the methyl branches partial interdigitation is observed. In the case of bolaamphiphiles, methyl side groups have a similar effect on the fluidity, but interdigitation cannot occur

The impact of alkyl chain purity on lipid based nucleic acid delivery systems – is the utilization of lipid components with technical grade justified?

The physicochemical properties and transfection efficacies of two samples of a cationic lipid have been investigated and compared in 2D (monolayers at the air/liquid interface) and 3D (aqueous bulk dispersions) model systems using different techniques. The samples differ only in their chain composition due to the purity of the oleylamine (chain precursor). Lipid 8 (using the oleylamine of technical grade for cost-efficient synthesis) shows lateral phase separation in the Langmuir layers. However, the amount of attached DNA, determined by IRRAS, is for both samples the same. In 3D systems, lipid 8 p forms cubic phases, which disappear after addition of DNA. At physiological temperatures, both lipids (alone and in mixture with cholesterol) assemble to lamellar aggregates and exhibit comparable DNA delivery efficiency. This study demonstrates that non-lamellar structures are not compulsory for high transfection rates. The results legitimate the utilization of oleyl chains of technical grade in the synthesis of cationic transfection lipid

Simple cathode design for Li-S batteries : cell performance and mechanistic insights by in operando X-ray diffraction

Rechargeable batteries have been receiving increasing attention over the past several years, particularly with regard to the accelerated development of electric vehicles, but also for their potential in grid storage applications. Among the broad range of cathode active materials, elemental sulfur has the highest theoretical specific capacity, thereby making it one of the most promising positive electrode materials these days. In the present work, we show that already a simple cathode design (cathodes with a non-optimized composite microstructure) provides good electrochemical performance both in coin and pouch cells with sulfur loadings of 2 mg cm-2. Our research data demonstrate that (1) specific capacities of 1000 mA h g-1 can be achieved over 60 cycles at room temperature while the cyclability at elevated temperatures (here, theta > 40 [degree]C) is poor, (2) the discharge is the kinetically rate-limiting process, (3) the major fraction of active sulfur in the electrode is lost during the formation cycle at C/50 and (4) the Li-S cells suffer from drying-out due to continuous electrolyte decomposition on the lithium metal anode. In addition, in operando X-ray diffraction shows Li2S formation (grain size of <10 nm) on discharge and the appearance of single phase [small beta]-sulfur in the sub-100 nm size range - rather than the thermodynamically stable orthorhombic polymorph (alpha-sulfur) - by the end of the charge cycle

A Comparative Structural Study in Monolayers of GPI Fragments and Their Binary Mixtures

Glycosylphosphatidylinositols (GPIs), natural complex glycolipids essential for a range of biological functions, are poorly understood with regard to their interactions and arrangements in cellular membranes. To evaluate the role of the head group in the structure formation in 2D model membranes (monolayers formed at the soft air/liquid interface), we employed the highly surface sensitive grazing incidence X-ray diffraction technique to investigate three GPI-fragments bearing the same hydrophobic part but different head groups. Condensed monolayers of simple GPI fragments are defined only by ordered alkyl chains. The monolayers of more complex fragments are additionally characterized by highly ordered head groups. Due to the strong H-bond network formed by the head groups, GPI-fragment 3 both segregates and induces order into a model membrane phospholipid (POPC) that mimics the liquid-disordered phase of cell membranes. Here, we show that the strong van der Waals interactions between hydrophobic chains overcome the head group interactions and dominate the structure formation in mixtures of GPI-fragment 3 with lipids that form liquid-condensed phases. This behaviour can be linked to the GPIs affinity for the lipid rafts

Effect of chiral interactions on the structure of Langmuir monolayers

Structural changes in monolayers of the enantiomer and the racemic mixture of 1-hexadecyl-glycerol with temperature and surface pressure variations are compared. On compression, both monolayers exhibit a variation of the tilt azimuth from the direction to the nearest neighbor to the next nearest neighbor. In the monolayer of the racemate, this variation occurs as a first order transition. In the monolayer of the enantiomer, the unit cell is oblique, and continuously passes from a state close to the low-pressure state of the racemate to a state close to its high-pressure state. The azimuths of the unit-cell distortion and that of the tilt remain almost equal to each other. The effect of chirality decreases when the temperature is increased. Structural changes are explained in detail within the framework of the Landau theory of phase transitions

Rigid urea and self-healing thiourea ethanolamine monolayers

A series of long-tail alkyl ethanolamine analogs containing amide-, urea-, and thiourea moieties was synthesized and the behavior of the corresponding monolayers was assessed on the Langmuir–Pockels trough combined with grazing incidence X-ray diffraction experiments and complemented by computer simulations. All compounds form stable monolayers at the soft air/water interface. The phase behavior is dominated by strong intermolecular headgroup hydrogen bond networks. While the amide analog forms well-defined monolayer structures, the stronger hydrogen bonds in the urea analogs lead to the formation of small three-dimensional crystallites already during spreading due to concentration fluctuations. The hydrogen bonds in the thiourea case form a two-dimensional network, which ruptures temporarily during compression and is recovered in a self-healing process, while in the urea clusters the hydrogen bonds form a more planar framework with gliding planes keeping the structure intact during compression. Because the thiourea analogs are able to self-heal after rupture, such compounds could have interesting properties as tight, ordered, and self-healing monolayers

Bilayer Properties of 1,3-Diamidophospholipids

A series of 1,3-diamido phosphocholines was synthesized, and their potential to form stable bilayers was investigated. Large and giant unilamellar vesicles produced from these new lipids form a wide variety of faceted liposomes. Factors such as cooling rates and the careful choice of the liposome preparation method influence the formation of facets. Interdigitation was hypothesized as a main factor for the stabilization of facets and effectively monitored by small-angle X-ray scattering measurements

Against the rules: pressure induced transition from high to reduced order

Envisioning the next generation of drug delivery nanocontainers requires more in- depth information on the fundamental physical forces at play in bilayer membranes. In order to achieve this, we combine chemical synthesis with physical–chemical analytical methods and probe the relationship between a molecular structure and its biophysical properties. With the aim of increasing the number of hydrogen bond donors compared to natural phospholipids, a phospholipid compound bearing urea moieties has been synthesized. The new molecules form interdigitated bilayers in aqueous dispersions and self-assemble at soft interfaces in thin layers with distinctive structural order. At lower temperatures, endothermic and exothermic transitions are observed during compression. The LC1 phase is dominated by an intermolecular hydrogen bond network of the urea moieties leading to a very high chain tilt of 52°. During compression and at higher temperatures, presumably this hydrogen bond network is broken allowing a much lower chain tilt of 35°. The extremely different monolayer thicknesses violate the two-dimensional Clausius–Clapeyron equation

Theory of monolayers with boundaries: Exact results and Perturbative analysis

Domains and bubbles in tilted phases of Langmuir monolayers contain a class of textures knows as boojums. The boundaries of such domains and bubbles may display either cusp-like features or indentations. We derive analytic expressions for the textures within domains and surrounding bubbles, and for the shapes of the boundaries of these regions. The derivation is perturbative in the deviation of the bounding curve from a circle. This method is not expected to be accurate when the boundary suffers large distortions, but it does provide important clues with regard to the influence of various energetic terms on the order-parameter texture and the shape of the domain or bubble bounding curve. We also look into the effects of thermal fluctuations, which include a sample-size-dependent effective line tension.Comment: replaced with published version, 21 pages, 16 figures include