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Time-resolved synchrotron small-angle X-ray scattering (SAXS) was used to study the structural changes during the osmotic shrinkage of a pharmacologically relevant liposomal drug delivery system. Sterically stabilized liposomes (SSLs) with a diameter of 100 nm and composed of hydrogenated soy phosphocholine, cholesterol and distearoyl-phosphoethanolamine-PEG 2000 prepared in a salt-free buffer were mixed with a buffered 0.3 M NaCl solution using a stopped flow apparatus. The changes in the liposome size and the bilayer structure were followed by using SAXS with a time resolution of 20 ms. A linear decrease in liposome size is observed during the first ~4 s of the osmotic shrinkage, which reveals a water permeability value of 0.215 (15) μm s-1. The change in the size of the liposomes upon the osmotic shrinkage is also confirmed by dynamic light scattering. After this initial step, broad correlation peaks appear on the SAXS curves in the q range of the bilayer form factor, which indicates the formation of bi- or oligolamellar structures. Freeze-fracture combined with transmission electron microscopy revealed that lens-shaped liposomes are formed during the shrinkage, which account for the appearance of the quasi-Bragg peaks superimposed on the bilayer form factor. On the basis of these observations, it is proposed that the osmotic shrinkage of SSLs is a two-step process: in the initial step, the liposome shrinks in size, while the area/lipid adapts to the decreased surface area, which is then followed by the deformation of the spherical liposomes into lens-shaped vesicles. [ABSTRACT FROM AUTHOR]

Polyurethanes were prepared from 4,4′-methylenebis(phenyl isocyanate), 1,4-butanediol and poly(1,4-butanediol adipate) polyester polyol. The hydroxyl functional group ratio of polyol/total diol was kept constant at 0.4, while the ratio of the isocyanate and hydroxyl groups (NCO/OH ratio) changed between 0.90 and 1.15. The polymers were prepared by one-step bulk polymerization in an internal mixer. They were characterized using a number of methods including Fourier transform infrared spectroscopy, wide- and small-angle X-ray scattering, differential scanning calorimetry, dynamic mechanical analysis, light transmittance and tensile testing. Changing the stoichiometry modifies the molecular weight in accordance with the laws of stepwise polymerization, and the relative concentration of end groups also changes at the same time. Competitive interactions among various groups including chain-end functional groups lead to the formation of slightly ordered phases of sub-nanometre size at both ends of the composition range. These structures assemble into larger units at the 10 nm level, which associate further to even larger entities of micrometre size causing scattering of light and a decreased transparency of the samples. The order of the primary units, together with the number and size of assemblies at both higher levels, decrease as the composition approaches equimolar stoichiometry. The amount of less ordered amorphous phase has a maximum in this range. The stiffness of the polymers is determined by the amount of this phase, while ultimate properties are influenced also by molecular weight and the number of physical crosslinks formed. Copyright © 2010 Society of Chemical Industry Correlation between the tensile modulus and Flory-Huggins interaction parameter determined from ethanol uptake of polyurethane elastomer samples studied in the work reported. [ABSTRACT FROM AUTHOR]

Abstract: Three series of activated carbon monoliths have been prepared from logs of different trees (spruce (Picea abies), beech (Fagus silvatica), oak (Quercus robur)) by pyrolization in nitrogen flow at 700°C and then by steam activation at 900°C for different duration of the conversion. The characterization of carbon skeleton in the samples was performed by small angle X-ray scattering (SAXS), atomic force microscopy (AFM) and scanning electronmicrography (SEM). The carbonized xylem retained the original tracheal structure of the wood. Biological diversity of wood precursors reflected in the nanometer range likewise than in micrometer range. The evolution of the microporosity has been followed by static gas adsorption (N2 at −196°C). The characterization of dynamic adsorption properties took advantage of the unique potentials of the frequency response (FR) technique (N2 or O2 at −78°C). The obtained three-dimensional carbon frames exhibit low transport diffusional resistance due to the wide straight transport channels of micron size. All of the three wood types displayed nearly identical dependence of burn-off upon activation time, which in view of their similar cellulose composition, is not entirely unexpected. The shape of the isotherms indicates the presence of both micro and mesopores and the history of the activation is crucial for the developing porosity. The changes in the adsorption capacities of micropores reflect the differences of precursors and length of activation time. Compared to other methods FR technique seems to be more sensitive to distinguish such differences. [Copyright &y& Elsevier]

Abstract: The effect of Salmonella minnesota R595 lipopolysaccharide (LPS) on model membrane consisting of a mixture of fully hydrated lipids (dipalmitoylphosphatidylethanolamine (DPPE) and dipalmitoylglycerol (DPG)) was investigated by differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and freeze–fracture methods. The DPPE–DPG/water system forms a multilamellar arrangement in the gel phase which transforms into a mixture of inverted hexagonal and cubic structures. By the presence of LPS the thermotropic behaviour of the system was affected significantly only at its high concentration (1:1mol/mol LPS/DPPE–DPG) in the gel phase, while above the chain melting transition the ratio of the inverted cubic and the hexagonal structures was changed and at the 1:1mol/mol LPS/DPPE–DPG ratio a complex and amorphous phase was formed. The structural parameters of the inverted hexagonal and cubic phases are modified by the temperature and also by the LPS concentration, as deduced from the characteristic SAXS curves. Summarizing the effects of the LPS molecules on the DPPE–DPG/water vesicle system a schematic phase diagram was constructed. [Copyright &y& Elsevier]

The formation of copper hydroxide and copper oxide particles in the gaps among the stacks of multilamellar vesicles is described, illustrating a new pathway in the preparation of nanometre-scale particles. The in situ structural characterization of both the solid particles and the vesicles as a reaction medium was performed in the initial and final states of the process by using anomalous small-angle X-ray scattering (ASAXS) and freeze-fracture methods. The ASAXS method provides a description of the particle-size distribution of the copper nanoparticles, in spite of the fact that they are present in low concentration. This method allows the particle formation and growth to be monitored throughout the whole time range of the synthesis. [ABSTRACT FROM AUTHOR]

Extracellular vesicles isolated by differential centrifugation from Jurkat T-cell line were investigated by attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR). Amide and C H stretching band intensity ratios calculated from IR bands, characteristic of protein and lipid components, proved to be distinctive for the different extracellular vesicle subpopulations. This proposed ‘spectroscopic protein-to-lipid ratio’, combined with the outlined spectrum-analysis protocol is valid also for low sample concentrations (0.15–0.05 mg/ml total protein content) and can carry information about the presence of other non-vesicular formations such as aggregated proteins, lipoproteins and immune complexes. Detailed analysis of IR data reveals compositional changes of extracellular vesicles subpopulations: second derivative spectra suggest changes in protein composition from parent cell towards exosomes favoring proteins with β-turns and unordered motifs at the expense of intermolecular β-sheet structures. The IR-based protein-to-lipid assessment protocol was tested also for red blood cell derived microvesicles for which similar values were obtained. The potential applicability of this technique for fast and efficient characterization of vesicular components is high as the investigated samples require no further preparations and all the different molecular species can be determined in the same sample. The results indicate that ATR-FTIR measurements provide a simple and reproducible method for the screening of extracellular vesicle preparations. It is hoped that this sophisticated technique will have further impact in extracellular vesicle research. [ABSTRACT FROM AUTHOR]

Extracellular vesicles (EVs), sub-micrometer lipid-bound particles released by most cells, are considered a novel area in both biology and medicine. Among characterization methods, infrared (IR) spectroscopy, especially attenuated total reflection (ATR), is a rapidly emerging label-free tool for molecular characterization of EVs. The relatively low number of vesicles in biological fluids (∼10 10 particle/mL), however, and the complex content of the EVs' milieu (protein aggregates, lipoproteins, buffer molecules) might result in poor signal-to-noise ratio in the IR analysis of EVs. Exploiting the increment of the electromagnetic field at the surface of plasmonic nanomaterials, surface-enhanced infrared spectroscopy (SEIRS) provides an amplification of characteristic IR signals of EV samples. Negatively charged citrate-capped and positively charged cysteamine-capped gold nanoparticles with around 10 nm diameter were synthesized and tested with blood-derived EVs. Both types of gold nanoparticles contributed to an enhancement of the EVs' IR spectroscopic signature. Joint evaluation of UV-Vis and IR spectroscopic results, supported by FF-TEM images, revealed that proper interaction of gold nanoparticles with EVs is crucial, and an aggregation or clustering of gold nanoparticles is necessary to obtain the SEIRS effect. Positively charged gold nanoparticles resulted in higher enhancement, probably due to electrostatic interaction with EVs, commonly negatively charged., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Self-assembling peptides offer a versatile set of tools for bottom-up construction of supramolecular biomaterials. Among these compounds, non-natural peptidic foldamers experience increased focus due to their structural variability and lower sensitivity to enzymatic degradation. However, very little is known about their membrane properties and complex oligomeric assemblies - key areas for biomedical and technological applications. Here we designed short, acyclic β 3 -peptide sequences with alternating amino acid stereoisomers to obtain non-helical molecules having hydrophilic charged residues on one side, and hydrophobic residues on the other side, with the N-terminus preventing formation of infinite fibrils. Our results indicate that these β-peptides form small oligomers both in water and in lipid bilayers and are stabilized by intermolecular hydrogen bonds. In the presence of model membranes, they either prefer the headgroup regions or they insert between the lipid chains. Molecular dynamics (MD) simulations suggest the formation of two-layered bundles with their side chains facing opposite directions when compared in water and in model membranes. Analysis of the MD calculations showed hydrogen bonds inside each layer, however, not between the layers, indicating a dynamic assembly. Moreover, the aqueous form of these oligomers can host fluorescent probes as well as a hydrophobic molecule similarly to e.g. lipid transfer proteins. For the tested, peptides the mixed chirality pattern resulted in similar assemblies despite sequential differences. Based on this, it is hoped that the presented molecular framework will inspire similar oligomers with diverse functionality., (This journal is © The Royal Society of Chemistry 2020.)

A shear cell was constructed in two variants for simultaneous small-angle X-ray scattering and freeze fracture. Using this cell, the changes in the layer structure and the domain formation of the Synperonic A7-water system were investigated under shear. The reconstructions of both the layer and domain structures were not observed in the steady state after 1 h (following a 2 h long shear period). Destruction of the lamellar arrangement and formation of aggregates occurred during the stress. It was concluded that the tixotropic behavior originates rather from the change of the domain structure with a typical size range of microm than from the changes of the inner structure of domains with lamellar arrangement.