Nanoscale Structure of the Oil-Water Interface.

X-ray reflectivity (XR) and atomistic molecular dynamics (MD) simulations, carried out to determine the structure of the oil-water interface, provide new insight into the simplest liquid-liquid interface. For several oils (hexane, dodecane, and hexadecane) the XR shows very good agreement with a monotonic interface-normal electron density profile (EDP) broadened only by capillary waves. Similar agreement is also found for an EDP including a sub-Å thick electron depletion layer separating the oil and the water. The XR and MD derived depletions are much smaller than reported for the interface between solid-supported hydrophobic monolayers and water.

Structure and Volta potential of lipid multilayers: effect of X-ray irradiation.

The effect of hard X-ray radiation on the structure and electrostatics of solid-supported lipid multilayer membranes is investigated using a scanning Kelvin probe (SKP) integrated with a high-energy synchrotron beamline to enable in situ measurements of the membranes' local Volta potential (V(p)) during X-ray structural characterization. The undulator radiation employed does not induce any detectable structural damage, but the V(p) of both bare and lipid-modified substrates is found to undergo strong radiation-induced shifts, almost immediately after X-ray exposure. Sample regions that are macroscopically distant (~cm) from the irradiated region experience an exponential V(p) growth with a characteristic time constant of several minutes. The V(p) variations occurring upon periodic on/off X-ray beam switching are fully or partially reversible depending on the location and time-scale of the SKP measurement. The general relevance of these findings for synchrotron-based characterization of biomolecular thin films is critically reviewed.

Unifying interfacial self-assembly and surface freezing.

X-ray investigations reveal that the monolayers formed at the bulk alkanol-sapphire interface are densely packed with the surface-normal molecules hydrogen bound to the sapphire. About 30-35 °C above the bulk, these monolayers both melt reversibly and partially desorb. This system exhibits balanced intermolecular and molecule-substrate interactions which are intermediate between self-assembled and surface-frozen monolayers, each dominated by one interaction. The phase behavior is rationalized within a thermodynamic model comprising interfacial interactions, elasticity, and entropic effects. Separating the substrate from the melt leaves the monolayer structurally intact.

Simultaneous small- and wide-angle scattering at high X-ray energies.

Combined small- and wide-angle X-ray scattering (SAXS/WAXS) is a powerful technique for the study of materials at length scales ranging from atomic/molecular sizes (a few angstroms) to the mesoscopic regime ( approximately 1 nm to approximately 1 microm). A set-up to apply this technique at high X-ray energies (E > 50 keV) has been developed. Hard X-rays permit the execution of at least three classes of investigations that are significantly more difficult to perform at standard X-ray energies (8-20 keV): (i) in situ strain analysis revealing anisotropic strain behaviour both at the atomic (WAXS) as well as at the mesoscopic (SAXS) length scales, (ii) acquisition of WAXS patterns to very large q (>20 A(-1)) thus allowing atomic pair distribution function analysis (SAXS/PDF) of micro- and nano-structured materials, and (iii) utilization of complex sample environments involving thick X-ray windows and/or samples that can be penetrated only by high-energy X-rays. Using the reported set-up a time resolution of approximately two seconds was demonstrated. It is planned to further improve this time resolution in the near future.

Time-resolved SAXS study of the effect of a double hydrophilic block-copolymer on the formation of CaCO3 from a supersaturated salt solution.

The effect of a double hydrophilic block-copolymer additive (made of polyaspartic acid and polyethyleneglycol, pAsp(10)-b-PEG(110)) on the initial formation of calcium carbonate from a supersaturated salt solution has been studied in situ by means of time-resolved synchrotron small-angle X-ray scattering (SAXS). A stopped-flow cell was used for rapidly mixing the 20 mM aqueous reactant solutions of calcium chloride and sodium carbonate. In reference measurements without polymer additive the very rapid formation of primary, overall spherical CaCO(3) particles with a radius of ca. 19 nm and a size polydispersity of ca. 26% was observed within the first 10 ms after mixing. A subsequent, very rapid aggregation of these primary particles was evidenced by a distinct upturn of the SAXS intensity at smallest angles. During the aggregation process the size of the primary particles remained unchanged. From an analysis of the absolute scattering intensity the mass density of these particles was determined to 1.9 g/cm(3). From this rather low density it is concluded that those precursor particles are amorphous, which has been confirmed by simultaneous wide-angle X-ray diffraction measurements. Upon adding 200 pm of the block-copolymer no influence on the size, the size polydispersity and morphology of the primary particles, nor on the kinetics of their formation and growth, was found. On the other hand, the subsequent aggregation and precipitation process is considerably slowed down by the additive and smaller aggregates result. The crystalline morphology of the sediment was studied in situ by WAXS ca. 50 min after mixing the reactants. Several diffraction rings could be detected, which indicate that a transformation of the metastable, amorphous precursor particles to randomly oriented vaterite nanocrystallites has taken place. In addition, a few isolated Bragg spots of high intensity were detected, which are attributed to individual, oriented calcite microcrystals that nucleated at the wall of the capillary.

Microstructure and dynamics near an attractive colloidal glass transition.

The microstructure and dynamics of a colloidal system interacting via short-ranged interparticle potential is studied by ultra-small-angle x-ray scattering and x-ray photon correlation spectroscopy. A colloidal gas-liquid type transition is induced when the short-ranged attractive interactions attain sufficient magnitude. The development of liquidlike structure is preceded by a systematic transition in the particle dynamics from diffusive to constrained motion and then completely frozen behavior. This demonstrates the existence of a jamming transition induced by strong short-ranged attractive interactions even at low packing fractions.

Mammography with synchrotron radiation: phase-detection techniques.

The authors evaluated the effect on mammographic examinations of the use of synchrotron radiation to detect phase-perturbation effects, which are higher than absorption effects for soft tissue in the energy range of 15-25 keV. Detection of phase-perturbation effects was possible because of the high degree of coherence of synchrotron radiation sources. Synchrotron radiation images were obtained of a mammographic phantom and in vitro breast tissue specimens and compared with conventional mammographic studies. On the basis of grades assigned by three reviewers, image quality of the former was considerably higher, and the delivered dose was fully compatible.

Low-dose phase contrast x-ray medical imaging.

Phase contrast x-ray imaging is a powerful technique for the detection of low-contrast details in weakly absorbing objects. This method is of possible relevance in the field of diagnostic radiology. In fact, imaging low-contrast details within soft tissue does not give satisfactory results in conventional x-ray absorption radiology, mammography being a typical example. Nevertheless, up to now all applications of the phase contrast technique, carried out on thin samples, have required radiation doses substantially higher than those delivered in conventional radiological examinations. To demonstrate the applicability of the method to mammography we produced phase contrast images of objects a few centimetres thick while delivering radiation doses lower than or comparable to doses needed in standard mammographic examinations (typically approximately 1 mGy mean glandular dose (MGD)). We show images of a custom mammographic phantom and of two specimens of human breast tissue obtained at the SYRMEP bending magnet beamline at Elettra, the Trieste synchrotron radiation facility. The introduction of an intensifier screen enabled us to obtain phase contrast images of these thick samples with radiation doses comparable to those used in mammography. Low absorbing details such as 50 microm thick nylon wires or thin calcium deposits (approximately 50 microm) within breast tissue, invisible with conventional techniques, are detected by means of the proposed method. We also find that the use of a bending magnet radiation source relaxes the previously reported requirements on source size for phase contrast imaging. Finally, the consistency of the results has been checked by theoretical simulations carried out for the purposes of this experiment.

Mammography of a phantom and breast tissue with synchrotron radiation and a linear-array silicon detector.

A linear-array, silicon pixel detector, capable of counting single photons, was applied to mammography by using a synchrotron radiation beam. Images were obtained of both a mammographic phantom and a breast-tissue sample. The phantom image was acquired with a mean glandular dose of 0.32 mGy. This detector combined with a synchrotron radiation beam allows acquisition of high-contrast, low-dose images of soft tissues.

A linear array silicon pixel detector: images of a mammographic test object and evaluation of delivered doses.

We present images of a mammographic test object obtained using a linear array silicon pixel detector capable of single-photon counting. The detector pixel size was 200 x 300 microns2 and images were acquired by scanning the test object between the laminar detector and the x-ray source with a scanning step of 100 microns. A molybdenum anode tube was used with two different filtrations: 2 mm aluminium and 25 microns molybdenum. Conventional film-screen images were also obtained in order to compare spatial and contrast resolution. In our digital images it is possible to recognize low-contrast details having dimensions smaller than or equal to the dimensions of details visible by means of a clinical mammographic unit. The detection of microcalcifications smaller than 150 microns was possible only when using the Mo filtration. However a copper wire of 50 microns diameter was detectable when embedded in a simulated tissue. We discuss in detail the mean glandular doses (MGDs) delivered during the image acquisition. The MGDs necessary to obtain good-quality images are always smaller than at a conventional mammographic unit. Since MGDs depend on the x-ray spectrum, the dose reduction becomes larger when the applied spectrum is harder than in film-screen acquisition (Al filtration and 35 kVp).