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G Brezesinski

Publications and source records attributed to G Brezesinski.

17 recordsLinked to original sources
PubMed2006

In-plane miscibility and mixed bilayer microstructure in mixtures of catanionic glycolipids and zwitterionic phospholipids.

SAXS/WAXS studies were performed in combination with freeze fracture electron microscopy using mixtures of a new Gemini catanionic surfactant (Gem16-12, formed by two sugar groups bound by a hydrocarbon spacer with 12 carbons and two 16-carbon chains) and the zwitterionic phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) to establish the phase diagram. Gem16-12 in water forms bilayers with the same amount of hydration water as DPPC. A frozen interdigitated phase with a low hydration number is observed below room temperature. The kinetics of the formation of this crystalline phase is very slow. Above the chain melting temperature, multilayered vesicles are formed. Mixing with DPPC produces mixed bilayers above the corresponding chain melting temperature. At room temperature, partially lamellar aggregates with local nematic order are observed. Splitting of infinite lamellae into discs is linked to immiscibility in frozen state. The ordering process is always accompanied by dehydration of the system. As a consequence, an unusual order-disorder phase transition upon cooling is observed.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2005

Biophysical and biochemical properties of a binary lipid mixture for DNA transfection.

The phase and miscibility behavior of a triple-chain phosphatidylcholine (TPHPC) and a single-chain surfactant (CTAB) were investigated in aqueous dispersions and in monolayers at the air/water interface. CTAB can be incorporated in the TPHPC monolayer because of its complementary molecule shape and reduces the tilt angle of TPHPC. The type of phases and the phase sequence (L2 - LS) are the same in the pure TPHPC monolayer and in the TPHPC/CTAB (80:20 mol:mol) mixture. No indication of any ordering of adsorbed DNA was observed. In the aqueous dispersions, TPHPC exhibits an inverted hexagonal phase above the chain melting. The addition of 30 mol% CTAB leads to the appearance of a lamellar Lalpha phase. The binding of DNA to the mixture is obvious but this is accompanied by a separation of the two lipids what is supported by monolayer experiments. The system has no long-term stability. The main reason seems to be not only the stronger interaction of DNA with CTAB, but also especially the unexpected weak interaction between CTAB and TPHPC. The transfection efficiency is lower compared with lipofectamine. The main disadvantage of this system is the cytotoxicity of CTAB, which could not be lowered by incorporation of CTAB in the TPHPC bilayer.

Animals↗
PubMed2004

Miscibility of DPPC and DPPA in monolayers at the air/water interface.

Monolayers of mixtures of 1,2-dipalmitoylphosphatidylcholine (DPPC) as the substrate and 1,2-dipalmitoylphosphatidic acid (DPPA) as the product of the hydrolysis reaction catalyzed by phospholipase D (PLD) were investigated in the presence of Ca2+. The miscibility behavior and the microstructure of mixed domains have been studied by grazing incidence X-ray diffraction (GIXD), Brewster angle microscopy and film balance measurements. The phase diagram reveals partial miscibility on both sides and a wide miscibility gap, which becomes narrower at high pressure. At low pressure, the segregation of condensed DPPA-rich domains in a fluid-like DPPC matrix was detected already at small DPPA concentrations and their structure was determined. A small amount of DPPC mixed into the segregated DPPA domains induces the transformation from rectangular to an oblique unit cell and increases the tilt angle in the condensed domains. At high pressure, two types of condensed phase domains were found: DPPC-rich and DPPA-rich. A drastic reduction of the tilt angle in the DPPC-rich domains with increasing amount of DPPA was observed. The decrease of the tilt angle must be connected with a change of the head group conformation of DPPC in such mixed domains.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2001

Structural analysis of a metallosupramolecular polyelectrolyte-amphiphile complex at the air/water interface.

A detailed analysis of a metallosupramolecular coordination polyelectrolyte-amphiphile complex (PAC) at the air/water interface is presented based on Langmuir isotherm measurements, Brewster angle microscopy as well as X-ray reflectance and diffraction measurements. The PAC is prepared in solution by metal-ion coordination of Fe(OAc)2 and 1,4-bis(2,2':6',2"-terpyridin-4'-yl)benzene followed by self-assembly with dihexadecyl phosphate (DHP). The spreading of the PAC at the air/water interface results in a Langmuir film with a stratified architecture, such that DHP forms a monolayer on the water surface, while the metallosupramolecular coordination polyelectrolyte (MEPE) is immersed in the aqueous subphase. Electrostatic interactions of MEPE and DHP force the alkyl chains into an upright, hexagonal lattice even at low surface pressures. This work illustrates how supramolecular, colloidal, and surface chemistry can be combined to create complex architectures with tailored characteristics that may not be accessible through self-organization in the liquid phase.

Journal Article↗
PubMed2001

Dipalmitoyl-phosphatidylcholine/phospholipase D interactions investigated with polarization-modulated infrared reflection absorption spectroscopy.

The hydrolysis of 1,2-dipalmitoylphosphatidylcholine (DPPC) catalyzed by Streptomyces chromofuscus phospholipase D (PLD) has been investigated using monolayer techniques and polarization-modulated infrared absorption reflection spectroscopy. The spectroscopic analysis of the phosphate groups provides a quantitative estimation of the hydrolysis yield. The hydrolysis kinetics was investigated in dependence on the phase state of the lipid monolayer. It was found that PLD exhibits maximum activity in the liquid-expanded phase, whereas PLA2 has its activity maximum in the two-phase region. A lag phase was observed in all experiments indicating that small amounts of the hydrolysis product 1,2-dipalmitoylphosphatidic acid (DPPA) are needed for initiating the fast hydrolysis reaction. Higher concentrations of DPPA inhibit the hydrolysis. The critical inhibition concentration of DPPA is a function of the monolayer pressure.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2001

X-ray diffraction and foam film investigations of PC head group interaction in water/ethanol mixtures.

The influence of ethanol on single phospholipid monolayers at the water/air interface and in foam films has been investigated. Grazing incidence X-ray diffraction investigations (GIXD) of Langmuir monolayers from 1,2-distearoyl-phosphatidylcholine (DSPC) spread on water subphases with different amounts of ethanol were performed. The thickness and free specific energy of formation of foam films stabilized by 1,2-dimyristoyl-phosphatidylcholine (DMPC) at different concentrations of ethanol in the film forming dispersions were measured. The GIXD investigations show that the tilt angle of the alkyl chains in the PC lipid monolayer decreases with increasing concentration of ethanol caused by a decrease of the diameter of the head groups. With increasing ethanol content of the solution also the thickness of the aqueous core of PC lipid foam films decreases. We assume that ethanol causes a decreasing probability for the formation of hydrogen bonds of water molecules to the PC head groups. The distinct difference between the effects of ethanol on lipid bilayers as described in the literature and on monolayers and foam films found in this study is discussed. Whereas PC monolayers at the water/air interface become unstable above 25 vol.% ethanol, the PC foam films are stable up to 50 vol.% ethanol. This is related to the decrease of the surface excess energy per lipid molecule by the interaction between the two film surfaces.

Ethanol↗
PubMed2000

Dynamic Observations of the Hydrolysis of a DPPC Monolayer at the Air/Water Interface Catalyzed by Phospholipase A(2) This work was supported by the research contract between the German Max-Planck-Society and the Chinese Academy of Sciences as well as the National Natural Science Foundation of China (NNSF). J.L. thanks the president fund of the Chinese Academy of Science and the National Personal Department of China. DPPC=L-dipalmitolphosphatidylcholine.

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Journal Article↗
PubMed1996

Chiral discrimination in a monolayer of a triple-chain phosphatidylcholine.

Monolayers of an enantiomeric and a racemic triple-chain phosphatidylcholine (PC) at the air/water interface are studied by film balance measurements and x-ray diffraction. Although the area per three tails exceeds that per head, we observe tail ordering dependent on headgroup chirality and chain tilt. This indicates lateral headgroup interactions. The influence of the chiral carbon is suppressed at higher lateral pressures, and a centered-rectangular unit cell with tails tilted into the nearest neighbor (NN) direction is observed for both the enantiomer and the racemate. The distortion of the lattice changes at medium pressures from NN to NNN (next-nearest neighbor direction) with decreasing temperature. The phase behavior of the racemate at 15 degrees C is compared with that of a triple-chain PC with a branched chain of reduced length. Whereas the PC with the longer branched chain exhibits only a NN tilted phase at all pressures, the PC with the shorter branched chain has a rich polymorphism (NNN-NN-upright hexagonal packing) under increased lateral pressure.

Biophysical Phenomena↗
PubMed1995

X-ray diffraction of a protein crystal anchored at the air/water interface.

We report the first successful in situ x-ray diffraction experiment with a 2D protein array at the lipid/water interface and demonstrate that the order can be controlled via lateral pressure or density. A protein (streptavidin) was bound to a monolayer of biotinylated lipid at the air/water interface, and diffraction of the protein layer could be measured to many orders. Compression of the monolayer changed the diffraction pattern drastically, indicating that the protein structure can be strongly influenced by external parameters like lateral pressure or density. From the width of the peaks, we find that aggregates consisting of as few as 100 monomers contribute to the diffraction. This indicates that the structure of even low order aggregates can be studied in situ. Grazing incidence diffraction can become a strong new method to study the crystallization and the interactions between proteins free from artifacts by staining or sample preparation.

Air↗
PubMed1994

Properties of unusual phospholipids: I. Synthesis, monolayer investigations and calorimetry of diacylglycerophosphocholines containing monoacetylenic acyl chains.

Isomeric diacylglycerophosphocholines containing various octadecynoic acids (4-, 6-, 9-, 12-, 14- and 17-octadecynoic acid) were synthesized and purified to homogeneity. Their behaviour in monolayers, when studied by the Langmuir-Blodgett film balance technique, revealed systematic relationships between structure and packing properties. The thermotropic phase behaviour of these novel phospholipids, as measured by differential scanning calorimetry, depended in a systematic fashion on the position of the triple bond: the gel-to-liquid-crystalline phase transition temperature (Tm) passed through a minimum of -3.4 degrees C for a triple bond in position 9.

Calorimetry, Differential Scanning↗
PubMed1994

Convex-concave curvatures in bilayers of dipalmitoylphosphatidylcholine and cholesterol induced by amphotericin B/deoxycholate after prolonged storage.

Freeze-fracture investigations on the influence of amphotericin B/deoxycholate on multilamellar vesicles (MLV) of DPPC containing cholesterol have revealed a new phase structure. Alternating convex and concave curvatures are observed after storage of the vesicles at temperatures below 25 degrees C for at least 4 weeks. Three types of these patterns occur, a small-dimensional (repeat distance approximately 100 nm), an intermediate-dimensional (repeat distance approximately 400 nm) and a large-dimensional (repeat distance approximately 700 nm). The types can be formed on the same bilayer side by side. Additionally, the types differ in the morphology of the tops. In the case of the small-dimensional type the shape of the top can be described as a circular flat plane or opening and in the other cases as a hemispherical cap. The large dimensional type differs from the others by involvement of bilayer stacks. The formation of this new phase after prolonged storage could be confirmed by DSC measurements. The new structure can be explained in the framework of bicontinuous cubic phases and periodically curved bilayer structures. From the electron micrographs a lo (liquid ordered) phase is suggested.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed1988

Phase diagrams of pseudo-binary phospholipid systems. I. Influence of the chain length differences on the miscibility properties of cephaline/cephaline/water systems.

The miscibility properties of homologous cephalines (PEs) were studied by means of differential scanning calorimetry (DSC). The phase diagrams of 5 pseudo-binary cephaline/cephaline/water systems (50% water) are discussed. In the high temperature L alpha-phase, all the homologous cephalines of fatty acid chain length from C = 12 to C = 18 were completely miscible. On the other hand in the low temperature L beta-phase, a miscibility gap occurred in dependence on the differences of the acyl chain lengths. Further, a distinct succession of the phase diagram types was observed according to increasing chain length differences of the PEs: complete miscibility (systems di-(C12:O)-PE/di-(C14:O)-PE/H2O; di-(C14:O)-PE/di-C(16:O)-PE/H2O)----peritectic mixing behaviour (systems di-(C12:O)-PE/di-(C16:O)-PE/H2O; di-(C14:O)-PE/di-(C18:O)-PE/H2O)----eutectic mixing behaviour (system di-(C12:O)-PE/di-(C18:O)-PE/H2O). The change in the type of phase diagram from azeotropic to semi-azeotropic and from semi-azeotropic to eutectic is interpreted by means of the Landau theory.

Calorimetry, Differential Scanning↗
PubMed1986

Synthesis, calorimetry, and X-ray diffraction of lecithins containing branched fatty acid chains.

Lecithins with branched fatty acid chains were synthesized and characterized by differential scanning calorimetry and X-ray diffraction. The influence of three chemical alterations on the phase transition parameters were investigated: length of the branches in 2-position of the acyl chains, position of the branches in the acyl chains, and position of the branched fatty acid chains in the glycerol backbone. The results show that the branched phosphatidylcholines (PCs) have a reduced gel-to-liquid-crystalline phase transition temperature (Tm) compared to the corresponding straight-chain PCs. Depending on both the length of the branches in 2-position of the acyl chains and the position of the branches in the acyl chains, the Tm-values pass through a minimum. The systematic change of the main-transition temperatures Tm is connected with a modified structural polymorphism. If the length of the branches increases three types of polymorphism were observed.

Calorimetry, Differential Scanning↗
PubMed1982

Optical detection of phase transitions in simple and mixed lipid-water phases.

A simple method for the detection of phase transitions in lipid-water systems by recording the intensity of the transmitted light through a sample placed between crossed polarizers as a function of the temperature was developed. A very small amount of lipid material is sufficient for its effective application. Two zwitterionic lipids in water, dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine (DPPE) as well as their mixtures were studied by means of this method. The results were compared with differential scanning calorimetry (DSC) data and a good correspondence was established. A phase diagram of the DPPC-DPPE mixture is constructed. This study also throws additional light on the nature of the 'pretransition' of DPPC.

Birefringence↗
PubMedDate not supplied

Domain formation in monolayers.

For phospholipids at the air/water interface we demonstrate that molecular chirality in some, but not in all, cases influences the domain shapes. In other cases chirality in the head group region can cause a chiral structure considering the tail arrangement. This indicates head group ordering. Minute changes of the molecular structure may change domain morphology from circular to dendritic. This can be related to slight changes of the lattice structure. In case of a dendritic domain the chains are more tilted, the deviation from hexagonal symmetry is more pronounced, and hence the lattice anisotropy is larger. This can be understood also in view of recent simulations considering diffusion-limited aggregation models. In experiments at the oil/water interface we show that the electrostatic repulsion between domains is reduced by exchanging air against oil. Also line tension is reduced which can be understood by means of simple molecular models. The oil may penetrate into domains of the ordered phase if it is aliphatic and exhibits the same chain length as the lipid. In other cases it is excluded from the ordered monolayer regions. Taking aliphatic dioles as the most simple models we show that head group chirality is expressed in domain shapes, and partly also in lattice structure.

Biophysical Phenomena↗