Rodlike Complexes of a Polyelectrolyte (Hyaluronan) and a Protein (Lysozyme) observed by SANS

We study by Small Angle Neutron Scattering (SANS) the structure of Hyaluronan -Lysozyme complexes. Hyaluronan (HA) is a polysaccharide of 9 nm intrinsic persistence length that bears one negative charge per disaccharide monomer (Mmol = 401.3 g/mol); two molecular weights, Mw = 6000 and 500 000 Da were used. The pH was adjusted at 4.7 and 7.4 so that lysozyme has a global charge of +10 and + 8 respectively. The lysozyme concentration was varied from 3 to 40 g/L, at constant HA concentration (10 g/L). At low protein concentration, samples are monophasic and SANS experiments reveal only fluctuations of concentration although, at high protein concentration, clusters are observed by SANS in the dense phase of the diphasic samples. In between, close to the onset of the phase separation, a distinct original scattering is observed. It is characteristic of a rod-like shape, which could characterize "single" complexes involving one or a few polymer chains. For the large molecular weight (500 000) the rodlike rigid domains extend to much larger length scale than the persistence length of the HA chain alone in solution and the range of the SANS investigation. They can be described as a necklace of proteins attached along a backbone of diameter one or a few HA chains. For the short chains (Mw ~ 6000), the rod length of the complexes is close to the chain contour length (~ 15 nm)

Small angle X-ray and neutron scattering: Powerful tools for studying the structure of drug-loaded liposomes

Nanovectors, such as liposomes, micelles and lipid nanoparticles, are recognized as efficient platforms for delivering therapeutic agents, especially those with low solubility in water. Besides being safe and non-toxic, drug carriers with improved performance should meet the requirements of (i) appropriate size and shape and (ii) cargo upload/release with unmodified properties. Structural issues are of primary importance to control the mechanism of action of loaded vectors. Overall properties, such as mean diameter and surface charge, can be obtained using bench instruments (Dynamic Light Scattering and Zeta potential). However, techniques with higher space and time resolution are needed for in-depth structural characterization. Small-angle X-ray (SAXS) and neutron (SANS) scattering techniques provide information at the nanoscale and have therefore been largely used to investigate nanovectors loaded with drugs or other biologically relevant molecules. Here we revise recent applications of these complementary scattering techniques in the field of drug delivery in pharmaceutics and medicine with a focus to liposomal carriers. In particular, we highlight those aspects that can be more commonly accessed by the interested users

Structure and spacing of cellulose microfibrils in woody cell walls of dicots

The structure of cellulose microfibrils in situ in wood from the dicotyledonous (hardwood) species cherry and birch, and the vascular tissue from sunflower stems, was examined by wide-angle X-ray and neutron scattering (WAXS and WANS) and small-angle neutron scattering (SANS). Deuteration of accessible cellulose chains followed by WANS showed that these chains were packed at similar spacings to crystalline cellulose, consistent with their inclusion in the microfibril dimensions and with a location at the surface of the microfibrils. Using the Scherrer equation and correcting for considerable lateral disorder, the microfibril dimensions of cherry, birch and sunflower microfibrils perpendicular to the [200] crystal plane were estimated as 3.0, 3.4 and 3.3 nm respectively. The lateral dimensions in other directions were more difficult to correct for disorder but appeared to be 3 nm or less. However for cherry and sunflower, the microfibril spacing estimated by SANS was about 4 nm and was insensitive to the presence of moisture. If the microfibril width was 3 nm as estimated by WAXS, the SANS spacing suggests that a non-cellulosic polymer segment might in places separate the aggregated cellulose microfibrils

Une brève introduction à la matière molle

A short introduction to soft condensed matter (polymers, colloids, surfactants) is presented, with particular emphasis to recent progres and applications of small angle scattering. The text is in French

A Neutron Scattering Study of the Structure of Poly(dimethylsiloxane)-Stabilized Poly(methyl methacrylate) (PDMS–PMMA) Latexes in Dodecane

Hard-sphere particles in nonpolar solvents are an essential tool for colloid scientists. Sterically stabilized poly(methyl methacrylate) (PMMA) particles have long been used as the exemplary hard-sphere system. However, neither the particles themselves nor the poly(12-hydroxystearic acid) (PHSA) stabilizer necessary to prevent aggregation in nonpolar solvents are commercially available. To counter this, several alternatives have been proposed. In recent years, there has been an increased interest in poly(dimethylsiloxane) (PDMS) stabilizers as a commercially available alternative to PHSA, yet the structure of particles made in this way is not as well understood as those produced using PHSA. In this work, we employ small-angle neutron scattering to determine the internal structure of PDMS-stabilized PMMA particles, synthesized with and without an additional crosslinking agent. We report data consistent with a homogeneous PMMA core with a linearly decaying PDMS shell. The thickness of the shell was in excess of 50 nm, thicker than the PHSA layer typically used to stabilize PMMA but consistent with reports of the layer thickness for similar molecular weight PDMS at planar surfaces. We also show that the amount of the hydrogenous material in the particle core of the crosslinked particles notably exceeds the amount of added ethylene glycol dimethacrylate crosslinker, suggesting some entrapment of the PDMS stabilizer in the PMMA matrix

Hemicellulose binding and the spacing of cellulose microfibrils in spruce wood

Cellulose microfibrils in conifers, as in other woody materials, are aggregated into loose bundles called macrofibrils. The centre-to-centre spacing of the microfibrils within these macrofibrils can be estimated from the position of a broad diffraction peak in small-angle neutron scattering (SANS) after deuteration. A known spacing of 3.0 nm, increasing with moisture content, is consistent with direct microfibril to microfibril contact. However recent evidence indicates that conifer microfibrils are partially coated with bound xylan chains, and possibly with lignin and galactoglucomannan, implying a wider centre-to-centre spacing as found in angiosperm wood. Delignification of spruce wood allowed a weak SANS peak to be observed without measurable change in spacing. By deuterating spruce wood in mildly alkaline D2O and then re-equilibrating with ambient H2O, deuterium atoms were trapped in a position that gave a 3.8 nm microfibril spacing under dry conditions as in angiosperm wood, instead of the 3.0 nm spacing normally observed in conifers. After conventional vapour deuteration of spruce wood a minor peak at 3.8 nm could be fitted in addition to the 3.0 nm peak. These observations are consistent with some microfibril segments being separated by bound xylan chains as in angiosperms, in addition to the microfibril segments that are in direct contact

A Novel Method for Studying the Dynamics of Confined Polymers in Nanoparticles in Nanoblends

The advances in new technologies have prompted the need for functional systems smaller than the gyration radius of polymer chains. Thus, understanding how nanoconfinement affects polymer properties has been the focus of a lot of research for over a decade. Polystyrene in particular has been reported to be strongly affected when nanoconfined as a thin film and specifically its glass transition temperature (Tg) is reported to decrease with decreasing film thickness. Tremendous effort has been dedicated to developing methods for quantifying the large-scale dynamic of nanoconfined polymers: film dewetting, film contraction, nanobubble inflation, nanoparticle imbedding and healing of deformed surfaces etc. In this work we describe a novel method to study the large scale dynamic and nanomechanical properties of nanoconfined polymers in nanoparticles in nanoblends. Nanoblends of dPS/PBMA were prepared from a mixture of colloidal suspensions of cross-linked PBMA and traces of dPS nanoparticles via water evaporation. The polymer blends were prepared at temperatures well below the glass transition of PS (TgPS) and above the Tg of cross-linked PBMA particles (TgPBMA). In these conditions we expect the PBMA particles to deform under capillary pressure to fill the interstices between them and the glassy PS nanoparticles to remain spherical. During the preparation of the nanoblends the elastic energy is stored within the deformed cross-linked PBMA nanoparticles. Upon annealing the films above TgPS, the PBMA nanoparticles regain their spherical shape and release the stored elastic energy, which induces the deformation of the PS nanoparticles. Small angle neutron scattering is then used to monitor the shape evolution of the PS nanoparticles and to quantify the relaxation dynamics of the polystyrene nanoparticles