Sigrid Bernstorff

First performance assessment of the small-angle X-ray scattering beamline at ELETTRA

The double-focusing high-flux wiggler beamline dedicated to small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) at ELETTRA has gone into user operation recently. It has been designed specifically for time-resolved studies of non-crystalline and fibrous materials in the submillisecond time scale, and has been optimized for small-angle scattering measurements. An overview of the beamline status and of some representative results, highlighting the performance of the SAXS beamline, are given.

The Importance of Protein-Protein Interactions on the pH-Induced Conformational Changes of Bovine Serum Albumin: A Small-Angle X-Ray Scattering Study

The combined effects of concentration and pH on the conformational states of bovine serum albumin (BSA) are investigated by small-angle x-ray scattering. Serum albumins, at physiological conditions, are found at concentrations of approximately 35-45 mg/mL (42 mg/mL in the case of humans). In this work, BSA at three different concentrations (10, 25, and 50 mg/mL) and pH values (2.0-9.0) have been studied. Data were analyzed by means of the Global Fitting procedure, with the protein form factor calculated from human serum albumin (HSA) crystallographic structure and the interference function described, considering repulsive and attractive interaction potentials within a random phase approximation. Small-angle x-ray scattering data show that BSA maintains its native state from pH 4.0 up to 9.0 at all investigated concentrations. A pH-dependence of the absolute net protein charge is shown and the charge number per BSA is quantified to 10(2), 8(1), 13(2), 20(2), and 26(2) for pH values 4.0, 5.4, 7.0, 8.0, and 9.0, respectively. The attractive potential diminishes as BSA concentration increases. The coexistence of monomers and dimers is observed at 50 mg/mL and pH 5.4, near the BSA isoelectric point. Samples at pH 2.0 show a different behavior, because BSA overall shape changes as a function of concentration. At 10 mg/mL, BSA is partially unfolded and a strong repulsive protein-protein interaction occurs due to the high amount of exposed charge. At 25 and 50 mg/mL, BSA undergoes some re-folding, which likely results in a molten-globule state. This work concludes by confirming that the protein concentration plays an important role on the pH-unfolded BSA state, due to a delicate compromise between interaction forces and crowding effects.

Characteristics of mineral particles in the human bone/cartilage interface.

Bone and cartilage consist of different organic matrices, which can both be mineralized by the deposition of nano-sized calcium phosphate particles. We have studied these mineral particles in the mineralized cartilage layer between bone and different types of cartilage (bone/articular cartilage, bone/intervertebral disk, and bone/growth cartilage) of individuals aged 54 years, 12 years, and 6 months. Quantitative backscattered electron imaging and scanning small-angle X-ray scattering at a synchrotron radiation source were combined with light microscopy to determine calcium content, mineral particle size and alignment, and collagen orientation, respectively. Mineralized cartilage revealed a higher calcium content than the adjacent bone (p<0.05 for all samples), whereas the highest values were found in growth cartilage. Surprisingly, we found the mineral platelet width similar for bone and mineralized cartilage, with the exception of the growth cartilage sample. The most striking result, however, was the abrupt change of mineral particle orientation at the interface between the two tissues. While the particles were aligned perpendicular to the interface in cartilage, they were oriented parallel to it in bone, reflecting the morphology of the underlying organic matrices. The tight bonding of mineralized cartilage to bone suggests a mechanical role for the interface of the two elastically different tissues, bone and cartilage.

Performance and First Results of the ELETTRA High‐Flux Beamline for Small‐Angle X‐ray Scattering

A new beamline for small-angle X-ray scattering (SAXS) has recently been constructed and is presently under final commissioning at the 2 GeV storage ring ELETTRA. It has been designed specifically for time-resolved studies of non-crystalline and fibrous materials and has been optimized for small-angle scattering measurements. The beamline operates with a SAXS resolution between 10 and about 1400 A in d spacing (at 8 keV) and has been optimized with respect to high flux at the sample [of the order of 1013 photons s−1 for 8 keV photons (2 GeV, 400 mA)]. Soon it will be possible to perform simultaneously wide-angle diffraction measurements in the d-spacing range 1.2–8 A (at 8 keV). In order to allow time-resolved (resolution ~1 ms) small-angle scattering measurements, a high-power 57-pole wiggler is used as the beamline source. From its beam, one of three discrete energies, 5.4, 8 and 16 keV, can be selected with a double-crystal monochromator, which contains three pairs of asymmetrically cut plane Si(111) crystals. Downstream, the beam is focused horizontally and vertically by a toroidal mirror. Commissioning tests of this new SAXS beamline showed that all design parameters have been realized.

A Closer Look into Two-Step Perovskite Conversion with X-ray Scattering

Recently, hybrid perovskites have gathered much interest as alternative materials for the fabrication of highly efficient and cost-competitive solar cells; however, many questions regarding perovskite crystal formation and deposition methods remain. Here we have applied a two-step protocol where a crystalline PbI2 precursor film is converted to MAPbI3-xClx perovskite upon immersion in a mixed solution of methylammonium iodide and methylammonium chloride. We have investigated both films with grazing incidence small-angle X-ray scattering to probe the inner film morphology. Our results demonstrate a strong link between lateral crystal sizes in the films before and after conversion, which we attribute to laterally confined crystal growth. Additionally, we observe an accumulation of smaller grains within the bulk in contrast with the surface. Thus, our results help to elucidate the crystallization process of perovskite films deposited via a two-step technique that is crucial for controlled film formation, improved reproducibility, and high photovoltaic performance.

New evidence for gel-liquid crystalline phase coexistence in the ripple phase of phosphatidylcholines

Abstract Experimental evidence supporting the hypothesis of gel-liquid crystalline phase coexistence in the stable ripple phase of diacylphosphatidylcholines has been obtained from time-resolved X-ray small- (SAXS) and wide-angle diffraction (WAXS) in the millisecond to second time domain. The pretransition of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) exhibits a thin lamellar liquid crystalline intermediate phase (designated Lα*) if driven far away from equilibrium by an infrared temperature jump (T-jump) technique. The findings can be described by a two-step model. (1) Instantaneously with the T-jump, an anomalously thin lamellar liquid crystalline intermediate phase (d = 5.6–5.8 nm) forms, coexisting with the original gel-phase Lβ′. Within the first seconds, the lamellar repeat distance of the intermediate increases to a value of about 6.7 nm. A closer examination of these kinetics reveals two relaxation components: a fast process, proceeding within tenths of a second, and a slow process, on the time scale of a few seconds. (2) Finally, both the liquid crystalline and the gel-phase relax into the stable ripple phase Pβ′. The total process time of the transition is nearly independent of the addition of NaCl, but varies strongly with the chain length of the lecithin species.

High-Throughput Asymmetric Double-Crystal Monochromator of the SAXS Beamline at ELETTRA

A new high-flux wiggler beamline for fast time-resolved small-angle X-ray scattering (SAXS) based on double-focusing optics has recently commenced operation at the 2 GeV third-generation storage ring ELETTRA at Trieste, Italy. Its non-dispersive double-crystal monochromator contains three pairs of interchangeable asymmetrically cut flat Si(111)-crystal pairs, each of which is optimized for high throughput at one of the three fixed energies 5.4, 8 and 16 keV. To cope with the severe thermal power load produced by a 57-pole wiggler on the first crystal of each pair (up to 5.4 W mm(-2) and 700 W under normal incidence, for 400 mA), grazing angles of 2 degrees and optimized back-cooling have been chosen. This solution allows simultaneously a gain of 2.5-3.0 in throughput and, accordingly, in flux density. Finite-element analysis as well as commissioning tests showed that the cooling layout functions very satisfactorily, and that up to 5 x 10(12) photons s(-1) are available at the sample (at 8 keV and 250 mA), as predicted.

Investigation of bone and cartilage by synchrotron scanning-SAXS and -WAXD with micrometer spatial resolution

Biological materials such as bone or wood are hierarchically structured to optimize mechanical and other properties. Several methods and experimental techniques are usually needed to study these materials on different length scales. We developed a device for small angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD), optimized for position resolved investigations of bone sections using synchrotron radiation. Thin samples can be scanned with 20 µm steps, acquiring two-dimensional SAXS or WAXD patterns at every point. The system was tested by performing one-dimensional scans across bone cartilage interfaces, revealing information about size, shape and orientation of nanometer sized mineral particles as well as about crystal type and texture of these particles.

Vacancy concentrations determined from the diffuse background scattering of X-rays in plastically deformed copper

The background intensity of X-ray diffraction patterns is analysed in terms of point defects, especially vacancies, in poly- and single-crystalline copper specimens. The samples have been deformed by compression in-situ in a synchrotron peak profile experiment. Systematic comparative analysis of X-ray, electrical resistivity, and calorimetric measurements indicate that (i) point defects, especially vacancies, are produced during plastic deformation and (ii) that the point defect concentration is increasing concomittantly with the actual dislocation density. The point defect production rate in poly- and single-crystalline specimens is observed to be drastically different. This difference is interpreted as different vacancy production rates in the grain interior and in the grain-boundary regions. With increasing deformation, the vacancy concentration in the grain-boundary regions is found to approach the equilibrium values corresponding to the melting temperature of copper. This result would support the assumption that in severely deformed metals the grain boundary region is a highly distorted, almost amorphous phase of the material.

In operando morphology investigation of inverted bulk heterojunction organic solar cells by GISAXS

Highly stable poly(3-hexylthiophene-2,5-diyl) (P3HT) : phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojunction solar cells are fabricated by using an inverted geometry. The direct correlation between the morphology of the active layer and the device performance during continuous operation under illumination is revealed by in operando grazing incidence small angle X-ray scattering (GISAXS) and I–V measurements. Other than in devices with normal geometry, it is found that the P3HT : PCBM active layer shows a stable morphology during early operation times, which leads to an improved stability of the short circuit current and accordingly the power conversion efficiency of the inverted solar cell. Furthermore, the inverted P3HT : PCBM solar cells are long-term stable without encapsulation if they are stored under ambient dark conditions. It reveals that the power conversion efficiency preserves around 88% of the initial value after more than 150 days.