The saponin aescin, a mixture of triterpenoid saponins, is obtained from the seeds of the horse chestnut tree Aesculus hippocastanum. The β-form employed in this study is haemolytically active. The ...haemolytic activity results from the ability of aescin to form strong complexes with cholesterol in the red blood cell membrane. In this study, we provide a structural analysis on the complex formation of aescin and cholesterol when embedded in a phospholipid model membrane formed by 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). In this work, the temperatures investigated extend from DMPC's L
to its L
phase in dependence of different amounts of the saponin (0-6 mol% for calorimetric and 0-1 mol% for structural analyses) and the steroid (1-10 mol%). At these aescin contents model membranes are conserved in the form of small unilamellar vesicles (SUVs) and major overall structural modifications are avoided. Additionally, interactions between aescin and cholesterol can be studied for both phase states of the lipid, the gel and the fluid state. From calorimetric experiments by differential scanning calorimetry (DSC), it could be shown that both, the steroid and the saponin content, have a significant impact on the cooperative phase transition behaviour of the DMPC molecules. In addition, it becomes clearly visible that the entire phase behaviour is dominated by phase separation which indeed also depends on the complexes formed between aescin and cholesterol. We show by various methods that the addition of cholesterol alters the impact of aescin on structural parameters ranging from the acyl chain correlation to vesicle-vesicle interactions. While the specific saponin-phospholipid interaction is reduced, addition of cholesterol leads to deformation of SUVs. The analyses of the structures formed were performed by wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS).
Full text
Available for:
IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Multicomponent supramolecular gels have great potential for optoelectronics. Ideally, we could control the self-assembly of multiple components across many length scales, from the primary assembled ...structures to how these are arranged in space. This would allow energy transfer between p-type and n-type fibers to be controlled. Usually, a single network is formed and analyzed. It is not clear how most networks could be modified, and certainly not how these might be differentiated. Here, we address both of these issues. We show how the different components in a multicomponent gel can be differentiated by small-angle neutron scattering using contrast-matching experiments. The rate of self-assembly can be used to vary the networks that are formed, leading directly to changes in the efficiency of electron transfer. The assembly kinetics can therefore be used to prepare different networks from the same primary building blocks and primary self-assembled structures. We expect that these advances will allow multicomponent systems to become effective electronic materials.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
Soft particles such as polymeric microgels can form ultra-dense phases, where the average center-to-center distance a
can be smaller than the initial unperturbed particle diameter σ
, due to their ...ability to interpenetrate and compress. However, despite of the effort devoted to microgels at ultrahigh densities, we know surprisingly little about their response to their environment at effective volume fractions ϕ
above close packing (ϕ
), and the existing information is often contradictory. Here we report direct measurements of the size and shape of poly(N-isopropylacrylamide) microgels at concentrations below and above ϕ
using the zero average contrast method in small-angle neutron scattering. We complement these experiments with measurements of the average interparticle distances using small-angle x-ray scattering, and a determination of the glass transition using dynamic light scattering. This allows us to unambiguously decouple interaction effects from density-dependent variations of the particle size and shape at all values of ϕ
. We demonstrate that the microgels used in this study significantly interpenetrate and thus change their size and shape only marginally even for ϕ
≫ ϕ
, a finding that may require changes in the interpretation of a number of previously published studies on the structural and dynamic properties of dense soft particle systems.
Full text
Available for:
IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Periodic superstructures of plasmonic nanoparticles have attracted significant interest because they can support coupled plasmonic modes, making them interesting for plasmonic lasing, metamaterials, ...and as light-management structures in thin-film optoelectronic devices. We have recently shown that noble metal hydrogel core–shell colloids allow for the fabrication of highly ordered 2-dimensional plasmonic lattices that show surface lattice resonances as the result of plasmonic/diffractive coupling (Volk, K.; Fitzgerald, J. P. S.; Ruckdeschel, P.; Retsch, M.; König, T. A. F.; Karg, M. Reversible Tuning of Visible Wavelength Surface Lattice Resonances in Self-Assembled Hybrid Monolayers. Adv. Optical Mater. 2017, 5, 1600971, DOI: 10.1002/adom.201600971). In the present work, we study the photonic properties and structure of 3-dimensional crystalline superstructures of gold hydrogel core–shell colloids and their pitted counterparts without gold cores. We use far-field extinction spectroscopy to investigate the optical response of these superstructures. Narrow Bragg peaks are measured, independently of the presence or absence of the gold cores. All crystals show a significant reduction in low-wavelength scattering. This leads to a significant enhancement of the plasmonic properties of the samples prepared from gold-nanoparticle-containing core–shell colloids. Plasmonic/diffractive coupling is not evident, which we mostly attribute to the relatively small size of the gold cores limiting the effective coupling strength. Small-angle neutron scattering is applied to study the crystal structure. Bragg peaks of several orders clearly assignable to an fcc arrangement of the particles are observed for all crystalline samples in a broad range of volume fractions. Our results indicate that the nanocrystal cores do not influence the overall crystallization behavior or the crystal structure. These are important prerequisites for future studies on photonic materials built from core–shell particles, in particular, the development of new photonic materials from plasmonic nanocrystals.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
Block copolymers were prepared with two anionic polyelectrolyte blocks: sodium polyacrylate (PA) and sodium polystyrene sulfonate (PSS), in order to investigate their phase behavior in aqueous ...solution in the presence of Ca
2+
cations. Depending on the concentration of polymer and Ca
2+
and on the ratio of the block lengths in the copolymer, spherical micelles were observed. Micelle formation arises from the specific interaction of Ca
2+
with the PA block only. An extensive small-angle scattering study was performed in order to unravel the structure and dimensions of the block copolymer micelles. Deuteration of the PA block enabled us to perform contrast variation experiments using small-angle neutron scattering at variable ratios of light and heavy water which were combined with information from small-angle X-ray scattering and dynamic light scattering.
Graphical Abstract
Block copolymers with two anionic polyelectrolyte blocks, sodium polyacrylate (PA) and sodium polystyrene sulfonate (PSS) self-assemble in response to an addition of Ca2+ cations. Deuteration of the PA block made possible contrast variation experiments using SANS at variable ratios of H2O/D2O, which in combination with SAXS revealed the morphology of the self-assemblies.
Full text
Available for:
EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OBVAL, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Multicomponent low molecular weight gels are useful for a range of applications. However, when mixing two components, both of which can independently form a gel, there are many potential scenarios. ...There is a limited understanding as to how to control and direct the assembly. Here, we focus on a pH-triggered two-component system. At high pH, colloidal structures are formed, and there is a degree of mixing of the two gelators. As the pH is decreased, there is a complex situation, where one gelator directs the assembly in a “sergeants and soldiers” manner. The second gelator is not fully incorporated, and the remainder forms an independent network. The result is that there is a nonlinear dependence on the final mechanical properties of the gels, with the storage or loss modulus being very dependent on the absolute ratio of the two components in the system.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
Electrostatic self-assembly of macroions is an emerging area with great potential in the development of nanoscale functional objects, where photo-irradiation responsiveness can either elevate or ...suppress the self-assembly. The ability to control the size and shape of macroion assemblies would greatly facilitate the fabrication of desired nano-objects that can be harnessed in various applications such as catalysis, drug delivery, bio-sensors, and actuators. Here, we demonstrate that a polyelectrolyte with a size of 5 nm and multivalent counterions with a size of 1 nm can produce well-defined nanostructures ranging in size from 10-1000 nm in an aqueous environment by utilizing the concept of electrostatic self-assembly and other intermolecular non-covalent interactions including dipole-dipole interactions. The
- and photoresponsiveness of polyelectrolytes and azo dyes provide diverse parameters to tune the nanostructures. Our findings demonstrate a facile approach to fabricating and manipulating self-assembled nanoparticles using light and neutron scattering techniques.
Full text
Available for:
IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Water interactions and accessibility of the nanoscale components of plant cell walls influence their properties and processability in relation to many applications. We investigated the ...water-accessibility of nanoscale pores within the fibrillar structures of unmodified Norway spruce cell walls by small-angle neutron scattering (SANS) and Fourier-transform infra-red (FTIR) spectroscopy. The different sensitivity of SANS to hydrogenated (
H
2
O
) and deuterated water (
D
2
O
) was utilized to follow the exchange kinetics of water among cellulose microfibrils. FTIR spectroscopy was used to study the time-dependent re-exchange of OD groups to OH in wood samples transferred from liquid
D
2
O
to
H
2
O
. In addition, the effects of drying on the nanoscale structure and its water-accessibility were addressed by comparing SANS results and the kinetics of water exchange between never-dried and dried/rewetted wood samples. The results of the kinetic analyses allowed to identify two processes with different timescales. The diffusion-driven exchange of water in the spaces between microfibrils, which was observed with both SANS and FTIR, takes place within minutes and rather homogeneously. The second, slower process appeared only in the OD/OH re-exchange followed by FTIR, and it still continued after several weeks of immersion in
H
2
O
. SANS could not detect any significant difference between the never-dried and dried/rewetted samples, whereas FTIR revealed a small portion of OD groups that resisted the re-exchange and this portion became larger with drying.
Graphic abstract
Full text
Available for:
EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Wood and other plant-based resources provide abundant, renewable raw materials for a variety of applications. Nevertheless, their utilization would greatly benefit from more efficient and accurate ...methods to characterize the detailed nanoscale architecture of plant cell walls. Non-invasive techniques such as neutron and X-ray scattering hold a promise for elucidating the hierarchical cell wall structure and any changes in its morphology, but their use is hindered by challenges in interpreting the experimental data. We used small-angle neutron scattering in combination with contrast variation by poly(ethylene glycol) (PEG) to identify the scattering contribution from cellulose microfibril bundles in native wood cell walls. Using this method, mean diameters for the microfibril bundles from 12 to 19 nm were determined, without the necessity of cutting, drying or freezing the cell wall. The packing distance of the individual microfibrils inside the bundles can be obtained from the same data. This finding opens up possibilities for further utilization of small-angle scattering in characterizing the plant cell wall nanostructure and its response to chemical, physical and biological modifications or even in situ treatments. Moreover, our results give new insights into the interaction between PEG and the wood nanostructure, which may be helpful for preservation of archaeological woods.
Full text
Available for:
IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Wood and other cellulosic materials are highly sensitive to changes in moisture content, which affects their use in most applications. We investigated the effects of moisture changes on the nanoscale ...structure of wood using X-ray and neutron scattering, complemented by dynamic vapor sorption. The studied set of samples included tension wood and normal hardwood as well as representatives of two softwood species. Their nanostructure was characterized in wet state before and after the first drying as well as at relative humidities between 15 and 90%. Small-angle neutron scattering revealed changes on the microfibril level during the first drying of wood samples, and the structure was not fully recovered by immersing the samples back in liquid water. Small and wide-angle X-ray scattering measurements from wood samples at various humidity conditions showed moisture-dependent changes in the packing distance and the inner structure of the microfibrils, which were correlated with the actual moisture content of the samples at each condition. In particular, the results implied that the degree of crystalline order in the cellulose microfibrils was higher in the presence of water than in the absence of it. The moisture-related changes observed in the wood nanostructure depended on the type of wood and were discussed in relation to the current knowledge on the plant cell wall structure.
Graphic abstract
Full text
Available for:
EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OBVAL, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
PDF
