Production of three-dimensional quantum dot lattice of Ge/Si core-shell quantum dots and Si/Ge layers in an alumina glass matrix.

We report on the formation of Ge/Si quantum dots with core/shell structure that are arranged in a three-dimensional body centered tetragonal quantum dot lattice in an amorphous alumina matrix. The material is prepared by magnetron sputtering deposition of Al2O3/Ge/Si multilayer. The inversion of Ge and Si in the deposition sequence results in the formation of thin Si/Ge layers instead of the dots. Both materials show an atomically sharp interface between the Ge and Si parts of the dots and layers. They have an amorphous internal structure that can be crystallized by an annealing treatment. The light absorption properties of these complex materials are significantly different compared to films that form quantum dot lattices of the pure Ge, Si or a solid solution of GeSi. They show a strong narrow absorption peak that characterizes a type II confinement in accordance with theoretical predictions. The prepared materials are promising for application in quantum dot solar cells.

Influence of annealing conditions on the formation of regular lattices of voids and Ge quantum dots in an amorphous alumina matrix.

In this work, the influence of air pressure during the annealing of Ge quantum dot (QD) lattices embedded in an amorphous Al(2)O(3) matrix on the structural, morphological and compositional properties of the film is studied. The formation of a regularly ordered void lattice after performing a thermal annealing process is explored. Our results show that both the Ge desorption from the film and the regular ordering of the QDs are very sensitive to the annealing parameters. The conditions for the formation of a void lattice, a crystalline Ge QD lattice and a disordered QD lattice are presented. The observed effects are explained in terms of oxygen interaction with the Ge present in the film.

SAXS/DSC/WAXD study of temperature evolution in nanocomposite polymer electrolytes with different nanofillers.

Polymer electrolytes are nanostructured materials which are very attractive components for batteries and opto-electronic devices. (PEO)8ZnCl2 polymer electrolytes were prepared from PEO and ZnCl2. The nanocomposites (PEO)8ZnCI2 themselves contained TiO2, Al2O3, MgO, ZnO and V2O5 nanograins. In this work, the influence of the Al2O3, MgO and V2O5 nanograins on the morphology and ionic conductivity of the nanocomposite was systematically studied by transmission small-angle X-ray scattering simultaneously recorded with wide-angle X-ray diffraction and differential scanning calorimetry at the synchrotron ELETTRA (Trieste, Italy). These three measurement methods yielded insight into the temperature-dependent changes of the grains of the electrolyte. The heating and cooling rate was 0.5 degrees C/min. Environment friendly galvanic cells as well as solar cells of the second generation are to be constructed with such nanocomposite polymer as electrolyte.

Nano Si superlattices for the next generation solar cells.

We present a study on amorphous SiO/SiO2 superlattice formation on Si substrate held at room temperature and annealed in the temperature range 600-1100 degrees C. Grazing-incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity were used to study such samples. Amorphous SiO/SiO2 superlattices were prepared by high vacuum physical vapor deposition of 4 nm thin films of SiO and SiO2 (10 layers each) from corresponding targets on silicon substrate. Rotation of the Si substrate during evaporation ensured homogeneity of the films over the whole substrate. We observed that the inhomogeneities introduced into the SiO and SiO2 layers during the deposition (evaporation) give rise to small angle scattering at lower annealing temperatures. After an initial SiO layer thickness reduction for 600 degrees C annealing, these thicknesses remain virtually unchanged up to 1000 degrees C, where they start to decrease again which leads to particle formation. Nevertheless, this compacting at low temperatures may lead to the seed formation in SiO layers that will facilitate later Si nanoparticles growth.

The influence of deposition temperature on the correlation of Ge quantum dot positions in amorphous silica matrix.

We studied the structural properties of (Ge+SiO2)/SiO2 multilayer films, especially the influence of the deposition temperature and the parameters of subsequent annealing on the formation and spatial correlation of Ge quantum dots in an amorphous silica matrix. We showed that in-layer and inter-layer spatial correlations of the formed Ge quantum dots strongly depend on the deposition temperature. For suitable chosen deposition parameters, highly correlated dot positions in all three dimensions can be obtained. It is demonstrated that the degree of the spatial correlation of quantum dots influences the size distribution width, which further affects the macroscopic properties of the quantum dot arrays.

Met-myoglobin association in dilute solution during pressure-induced denaturation: an analysis at pH 4.5 by high-pressure small-angle X-ray scattering.

In this paper, we report on the original global fit procedure of synchrotron small-angle X-ray scattering (SAXS) data applied to a model protein, met-myoglobin, in dilute solution during temperature- and pressure-induced denaturation processes at pH 4.5. Starting from the thermodynamic description of the protein unfolding pathway developed by Hawley (Hawley, S. A. Biochemistry 1971, 10, 2436), we have developed a new method for analyzing the set of SAXS curves using a global fitting procedure, which allows us to derive the form factor of all the met-myoglobin species present in the solution, their aggregation state, and the set of thermodynamic parameters, with their p and T dependence. This method also overcomes a reasonably poor quality of the experimental data, and it is found to be very powerful in analyzing SAXS data. SAXS experiments were performed at four different temperatures from hydrostatic pressures up to about 2000 bar. As a result, the presence of an intermediate, partially unfolded, dimeric state of met-myoglobin that forms during denaturation has been evidenced. The obtained parameters were then used to derive the met-myoglobin p, T phase diagram that fully agrees with the corresponding phase diagram obtained by spectroscopic measurements.

Effects of the number of actin-bound S1 and axial force on X-ray patterns of intact skeletal muscle.

Effects of the number of actin-bound S1 and of axial tension on x-ray patterns from tetanized, intact skeletal muscle fibers were investigated. The muscle relaxant, BDM, reduced tetanic M3 meridional x-ray reflection intensity (I(M3)), M3 spacing (d(M3)), and the equatorial I(11)/I(10) ratio in a manner consistent with a reduction in the fraction of S1 bound to actin rather than by generation of low-force S1-actin isomers. At complete force suppression, I(M3) was 78% of its relaxed value. BDM distorted dynamic I(M3) responses to sinusoidal length oscillations in a manner consistent with an increased cross-bridge contribution to total sarcomere compliance, rather than a changed S1 lever orientation in BDM. When the number of actin-bound S1 was varied by altering myofilament overlap, tetanic I(M3) at low overlap was similar to that in high [BDM] (79% of relaxed I(M3)). Tetanic d(M3) dependence on active tension in overlap experiments differed from that observed with BDM. At high BDM, tetanic d(M3) approached its relaxed value (14.34 nm), whereas tetanic d(M3) at low overlap was 14.50 nm, close to its value at full overlap (14.56 nm). This difference in tetanic d(M3) behavior was explicable by a nonlinear thick filament compliance which is extended by both active and passive tension.

In situ SAXS study on cationic and non-ionic surfactant liquid crystals using synchrotron radiation.

In situ synchrotron small-angle X-ray scattering was used to investigate various surfactant/water systems with hexagonal and lamellar structures regarding their structural behaviour upon heating and cooling. Measurements of the non-ionic surfactant Triton X-45 (polyethylene glycol 4-tert-octylphenyl ether) at different surfactant concentrations show an alignment of the lamellar liquid-crystalline structure close to the wall of the glass capillaries and also a decrease in d-spacing following subsequent heating/cooling cycles. Additionally, samples were subjected to a weak magnetic field (0.3-0.7 T) during heating and cooling, but no influence of the magnetic field was observed.

Myosin lever disposition during length oscillations when power stroke tilting is reduced.

M3 reflection intensity (I(M3)) from tetanized, intact skeletal muscle fiber bundles was measured during sinusoidal length oscillations at 2.8 kHz, a frequency at which the myosin motor's power stroke is greatly reduced. I(M3) signals were approximately sinusoidal, but showed a "double peak" distortion previously observed only at lower oscillation frequencies. A tilting lever arm model simulated this distortion, where I(M3) was calculated from the molecular structure of myosin subfragment 1 (S1). Simulations showed an isometric lever arm disposition close to normal to the filament axis at isometric tension, similar to that found using lower oscillation frequencies, where the power stroke contributes more toward total S1 movement. Inclusion of a second detached S1 in each actin-bound myosin dimer increased simulated I(M3) signal amplitude and improved agreement with the experimental data. The best agreement was obtained when detached heads have a fixed orientation, insensitive to length changes, and similar to that of attached heads at tetanus plateau. This configuration also accounts for the variations in relative intensity of the two main peaks of the M3 reflection substructure after a length change. This evidence of an I(M3) signal distortion when power stroke tilting is suppressed, provided that a large enough amplitude of length oscillation is used, is consistent with the tilting lever arm model of the power stroke.

Synchrotron diffraction study of deformation mechanisms in mineralized tendon.

The high stiffness and toughness of biomineralized tissues are related to the material deformation mechanisms at different levels of organization, from trabeculae and osteons at the micrometer level to the mineralized collagen fibrils at the nanometer length scale. Quantitatively little is known about the sub-micrometer deformation mechanisms under applied load. Using a parallel-fibred mineralized tissue from the turkey leg tendon as a model for the mineralized collagen fibrils, we used in situ tensile testing with synchrotron x-ray diffraction to measure the average fibril deformation with applied external strain. Diffraction peak splitting occurred at large strains, implying an inhomogeneous elongation of collagen fibrils. Scanning electron microscopy measurements lead us to conclude that the inhomogeneous mineralization in mineralized tendon is at the origin of the high fracture strain.

Structure of self-assembled liposome-DNA-metal complexes.

We have studied the structural and morphological properties of the triple complex dioleoyl phosphatidylcholine (DOPC)-DNA-Mn2+ by means of synchrotron x-ray diffraction and freeze-fracture transmission electron microscopy. This complex is formed in a self-assembled manner when water solutions of neutral lipid, DNA, and metal ions are mixed, which represents a striking example of supramolecular chemistry. The DNA condensation in the complex is promoted by the metal cations that bind the polar heads of the lipid with the negatively charged phosphate groups of DNA. The complex is rather heterogeneous with respect to size and shape and exhibits the lamellar symmetry of the L(c)(alpha) phase: the structure consists of an ordered multilamellar assembly similar to that recently found in cationic liposome-DNA complexes, where the hydrated DNA helices are sandwiched between the liposome bilayers. The experimental results show that, at equilibrium, globules of the triple complex in the L(c)(alpha) phase coexist with globules of multilamellar vesicles of DOPC in the L(alpha) phase, the volume ratio of the two structures being dependent on the molar ratio of the three components DOPC, DNA, and Mn2+. These complexes are of potential interest for applications as synthetically based nonviral carriers of DNA vectors for gene therapy.

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.

Viscoelastic properties of collagen: synchrotron radiation investigations and structural model.

Collagen type I is the most abundant structural protein in tendon, skin and bone, and largely determines the mechanical behaviour of these connective tissues. To obtain a better understanding of the relationship between structure and mechanical properties, tensile tests and synchrotron X-ray scattering have been carried out simultaneously, correlating the mechanical behaviour with changes in the microstructure. Because intermolecular cross-links are thought to have a great influence on the mechanical behaviour of collagen, we also carried out experiments using cross-link-deficient tail-tendon collagen from rats fed with beta-APN, in addition to normal controls. The load-elongation curve of tendon collagen has a characteristic shape with, initially, an increasing slope, corresponding to an increasing stiffness, followed by yielding and then fracture. Cross-link-deficient collagen produces a quite different curve with a marked plateau appearing in some cases, where the length of the tendon increases at constant stress. With the use of in situ X-ray diffraction, it was possible to measure simultaneously the elongation of the collagen fibrils inside the tendon and of the tendon as a whole. The overall strain of the tendon was always larger than the strain in the individual fibrils, which demonstrates that some deformation is taking place in the matrix between fibrils. Moreover, the ratio of fibril strain to tendon strain was dependent on the applied strain rate. When the speed of deformation was increased, this ratio increased in normal collagen but generally decreased in cross-link-deficient collagen, correlating to the appearance of a plateau in the force-elongation curve indicating creep. We proposed a simple structural model, which describes the tendon at a hierarchical level, where fibrils and interfibrillar matrix act as coupled viscoelastic systems. All qualitative features of the strain-rate dependence of both normal and cross-link-deficient collagen can be reproduced within this model. This complements earlier models that considered the next smallest level of hierarchy, describing the deformation of collagen fibrils in terms of changes in their molecular packing.

Frequency-dependent distortion of meridional intensity changes during sinusoidal length oscillations of activated skeletal muscle.

Bundles of intact, tetanized skeletal muscle fibers from Rana temporaria were subjected to sinusoidal length oscillations in the frequency domain 100 Hz to 3 kHz while measuring force and sarcomere length. Simultaneously, intensity of the third-order x-ray reflection of the axial myosin unit cell (I(M3)) was measured using synchrotron radiation. At oscillation frequencies <1 kHz, I(M3) was distorted during the shortening phase of the sinusoid (i.e., where bundle length was less than rest length). Otherwise, during the stretch phase of oscillations at all frequencies, during the shortening phase of oscillations above 1 kHz, and for bundles in the rigor state, I(M3) was approximately sinusoidal in form. Mean I(M3) during oscillations was reduced by 20% compared to the isometric value, suggesting a possible change in S1 disposition during oscillations. However, the amplitude of length change required to produce distortion (estimated from the phase angle at which distortion was first evident) corresponded to that of a step release sufficient to reach the maximum I(M3), indicating a mean S1 disposition during oscillations close to that during an isometric tetanus. The mechanical properties of the bundle during oscillations were also consistent with an unaltered S1 disposition during oscillations.

Collagen fibrils are differently organized in weight-bearing and not-weight-bearing regions of pig articular cartilage.

The magnetic resonance (MR) appearance of the weight-bearing ("loaded") and not-weight-bearing ("unloaded") regions in T(2)-weighted images of pig articular cartilage is different. On the hypothesis that this difference may be ascribed, at least in part, to a different collagen fibre organization in the two regions, this organization was studied using biochemical, histological, and X-ray diffraction methods. While the mean concentrations of collagen and of its cross-links were the same in the two regions, a regular small angle X-ray diffraction pattern was observed only for the habitually "loaded" tissue. It was also seen by light microscopy that the four typical functional zones were well displayed in the "loaded" cartilage whereas they were not clearly depicted in the "unloaded" tissue. Collagen presented a high concentration of fibrils forming an intricate and dense meshwork at the surface of both "loaded" and "unloaded" cartilage. A second zone of high collagen concentration was present at the upper layer of the deep zone of "loaded" cartilage. By contrast, this lamina of highly concentrated fibrils was lacking in "unloaded" cartilage and collagen fibrils appear thinner. Our study proves that the organization of collagen fibres is different for the "loaded" and "unloaded" regions of articular cartilage. It also suggests that this different organization may influence the MR appearance of the tissue. J. Exp. Zool. 287:346-352, 2000.

A combined mechanical and X-ray diffraction study of stretch potentiation in single frog muscle fibres.

The nature of the force (T) response during and after steady lengthening has been investigated in tetanized single muscle fibres from Rana temporaria (4 C; 2.15 micrometer sarcomere length) by determining both the intensity of the third order myosin meridional X-ray reflection (IM3) and the stiffness (e) of a selected population of sarcomeres within the fibre. With respect to the value at the isometric tetanus plateau (To), IM3 was depressed to 0.67 +/- 0.04 during steady lengthening at approximately 160 nm s(-1) (T approximately 1.7) and recovered to 0.86 +/- 0.05 during the 250 ms period of after-stretch potentiation following the rapid decay of force at the end of lengthening (T approximately 1.3); under the same conditions stiffness increased to 1.25 +/- 0.02 and to 1.12 +/- 0.03, respectively. After subtraction of the contribution of myofilaments to the half-sarcomere compliance, stiffness measurements indicated that (1) during lengthening the cross-bridge number rises to 1.8 times the original isometric value and the average degree of cross-bridge strain is similar to that induced by the force-generating process in isometric conditions (2.3 nm), and (2) after-stretch potentiation is explained by a residual larger cross-bridge number. Structural data are compatible with mechanical data if the axial dispersion of attached heads is doubled during steady lengthening and recovers half-way towards the original isometric value during after-stretch potentiation.

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

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 Lalpha) 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 Lbeta'. 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 Pbeta'. 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.

Fibrillar structure and mechanical properties of collagen.

Collagen type I is among the most important stress-carrying protein structures in mammals. Despite their importance for the outstanding mechanical properties of this tissue, there is still a lack of understanding of the processes that lead to the specific shape of the stress-strain curve of collagen. Recent in situ synchrotron X-ray scattering experiments suggest that several different processes could dominate depending on the amount of strain. While at small strains there is a straightening of kinks in the collagen structure, first at the fibrillar then at the molecular level, higher strains lead to molecular gliding within the fibrils and ultimately to a disruption of the fibril structure. Moreover, it was observed that the strain within collagen fibrils is always considerably smaller than in the whole tendon. This phenomenon is still very poorly understood but points toward the existence of additional gliding processes occurring at the interfibrillar level.

Studies on the 14.5 nm meridional X-ray diffraction reflection during length changes of intact frog muscle fibres.

The intensity of the 14.5 nm meridional reflection (M3) from activated skeletal muscle fibres was studied in both single fibres and fibre bundles during the imposition of length changes. During shortening at small load, the intensity of the reflection decreased within 2 ms to less than 20% of isometric intensity, then recovered partially during the remainder of the shortening. When shortening was terminated, recovery of intensity was delayed. Small shortening steps (0.5% fibre length) produced a fall in M3 intensity (IM3) delayed by ca. 250 microseconds compared to the fall in tension. For larger step releases (1% fibre length), the fall in IM3 was not delayed. The fall in IM3 could be almost completely reversed by a subsequent restretch applied within 1.5 ms. Beyond 10 ms after the initial release, the restretch caused a further fall in intensity. A rapid step stretch (0.5% fibre length) also caused a fall in IM3 without delay, which was partially reversed by a release applied within 10 ms. A second small release applied 3 ms (or less) after the first caused a second fall in M3 intensity, but without delay and with faster time course. Small amplitude sinusoidal length oscillations (0.15-0.2% sarcomere; 1 kHz) caused a sinusoidal change in M3 intensity, which was 180 degrees out of phase with the force oscillations, and lacked distortion during its release phase.

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.