Extreme ultraviolet transient gratings: A tool for nanoscale photoacoustics.

Collective lattice dynamics determine essential aspects of condensed matter, such as elastic and thermal properties. These exhibit strong dependence on the length-scale, reflecting the marked wavevector dependence of lattice excitations. The extreme ultraviolet transient grating (EUV TG) approach has demonstrated the potential of accessing a wavevector range corresponding to the 10s of nm length-scale, representing a spatial scale of the highest relevance for fundamental physics and forefront technology, previously inaccessible by optical TG and other inelastic scattering methods. In this manuscript we report on the capabilities of this technique in the context of probing thermoelastic properties of matter, both in the bulk and at the surface, as well as discussing future developments and practical considerations.

Characterization of organic compounds and drugs in sewage sludge aiming for agricultural recycling.

The application of sewage sludge in soils can bring benefits to agricultural productivity, however, the risks arising from this application must be measured and carefully evaluated. Persistent organics compounds and drugs can be present in the sewage sludge and if applied to the soil, they can cause severe risks to the soil biota and contamination of groundwater. This work determined 174 persistent organic compounds and drugs in sludge samples from a wastewater treatment plant using chromatographic methods. The drugs ciprofloxacin, enrofloxacin and diclofenac were quantified, and values varied according to sampling period. For persistent organic compounds, cresols were the most abundant compounds in sewage sludge. With the analyses made of both the elutriate and the filtrate, it was possible to verify the potential for soil retention or leaching that each compound can present with the application of sewage sludge in the agriculture.

Atomic scale investigation of the volume phase transition in concentrated PNIPAM microgels.

Combining elastic incoherent neutron scattering and differential scanning calorimetry, we investigate the occurrence of the volume phase transition (VPT) in very concentrated poly-(N-isopropyl-acrylamide) (PNIPAM) microgel suspensions, from a polymer weight fraction of 30 wt. % up to dry conditions. Although samples are arrested at the macroscopic scale, atomic degrees of freedom are equilibrated and can be probed in a reproducible way. A clear signature of the VPT is present as a sharp drop in the mean square displacement of PNIPAM hydrogen atoms obtained by neutron scattering. As a function of concentration, the VPT gets smoother as dry conditions are approached, whereas the VPT temperature shows a minimum at about 43 wt. %. This behavior is qualitatively confirmed by calorimetry measurements. Molecular dynamics simulations are employed to complement experimental results and gain further insights into the nature of the VPT, confirming that it involves the formation of an attractive gel state between the microgels. Overall, these results provide evidence that the VPT in PNIPAM-based systems can be detected at different time- and length-scales as well as under overcrowded conditions.

Disentangling time-focusing from beam divergence: A novel approach for high-flux thermal neutron spectroscopy at continuous and long-pulse sources.

We present the concept of a novel time-focusing technique for neutron spectrometers, which allows us to disentangle time-focusing from beam divergence. The core of this approach is a double rotating-crystal monochromator that can be used to extract a larger wavelength band from a white beam, thus providing a higher flux at the sample compared to standard time-of-flight instruments, yet preserving energy resolution and beam collimation. The performances of a spectrometer based on this approach are quantitatively discussed in terms of possible incident wavelengths, flux at the sample, and (Q, E)-resolution. Analytical estimates suggest flux gains of about one order of magnitude at comparable resolutions in comparison to conventional time-of-flight spectrometers. Moreover, the double monochromator configuration natively shifts the sample away from the source line-of-sight, thus significantly improving the signal-to-noise ratio. The latter, in combination with a system that does not increase the beam divergence, brings the further advantage of a cleaner access to the low-Q region, which is recognized to be of fundamental interest for magnetism and for disordered materials, from glasses to biological systems.

Lipid-mediated growth of SrCO3/CaCO3 hybrid films as bioactive coatings for Ti surfaces.

SrCO3 is frequently used as Sr2+ source in ceramic cements, but its application as bioactive coating for metallic implants has not been explored yet. Aiming at rapid osteointegration and because of the well-known Sr2+ effects on bone metabolism, researchers have sought to design Sr2+-containing biomaterials. In this context, developing simple techniques to prepare Sr2+-based coatings is a must nowadays. Here, we describe the use of a bioinspired lipid-mediated approach to grow SrCO3 hybrid films on Ti surfaces at room temperature. To obtain these coatings, we applied the Langmuir-Blodgett technique to deposit phospholipid films with high degree of organization on Ti. In this way, we expected that controlled SrCO3 crystal growth could be templated by the array of nucleation points arising from electrostatic interaction between Sr2+ and the phospholipid polar heads. To control surface composition and the amount of Sr2+ released from the coatings, we also promoted CaCO3 co-precipitation in the hybrid films. We characterized the hybrid coatings in terms of morphology, chemical structure, wettability, and ability to release Sr2+ upon immersion in biological medium. In vitro osteoblast culture on mixed SrCO3/CaCO3 films revealed that the osteogenic response depended on surface composition, as indicated by alkaline phosphatase activity overexpression, which is an early indicator of osteoblast differentiation. Results showed that the mixed SrCO3/CaCO3 hybrid film created a synergic environment for osteoblasts, and that proper Sr2+ release associated with a Ca2+-rich environment might have optimized the Sr2+ anabolic effect. In conclusion, we have proposed a bioinspired and versatile technique to grow hybrid films that can control surface composition and Sr2+ release. Our results open an opportunity to explore the use of SrCO3-based coatings for rapid metallic implant osteointegration.

All-DNA System Close to the Percolation Threshold.

We characterize via small-angle neutron scattering the structural properties of a mixture of all-DNA particles with functionalities 4 (A) and 2 (B) constrained by design to reside close to the percolation threshold. DNA base sequences are selected such that A particles can only bind with B ones and that at the studied temperature (10 °C) all AB bonds are formed and long-lived, originating highly polydisperse persistent equilibrium clusters. The concentration dependence of the scattered intensity and its wavevector dependence is exploited to determine the fractal dimension and the size distribution of the clusters, which are found to be consistent with the critical exponents of the 3-D percolation universality class. The value of DNA nanoparticles as nanometric patchy colloids with well-defined functionality, bonding selectivity, and exquisite control of the interaction strength is demonstrated.

Trace Metals in Soot and PM2.5 from Heavy-Fuel-Oil Combustion in a Marine Engine.

Heavy fuel oil (HFO) particulate matter (PM) emitted by marine engines is known to contain toxic heavy metals, including vanadium (V) and nickel (Ni). The toxicity of such metals will depend on the their chemical state, size distribution, and mixing state. Using online soot-particle aerosol mass spectrometry (SP-AMS), we quantified the mass of five metals (V, Ni, Fe, Na, and Ba) in HFO-PM soot particles produced by a marine diesel research engine. The in-soot metal concentrations were compared to in-PM2.5 measurements by inductively coupled plasma-optical emission spectroscopy (ICP-OES). We found that <3% of total PM2.5 metals was associated with soot particles, which may still be sufficient to influence in-cylinder soot burnout rates. Since these metals were most likely present as oxides, whereas studies on lower-temperature boilers report a predominance of sulfates, this result implies that the toxicity of HFO PM depends on its combustion conditions. Finally, we observed a 4-to-25-fold enhancement in the ratio V:Ni in soot particles versus PM2.5, indicating an enrichment of V in soot due to its lower nucleation/condensation temperature. As this enrichment mechanism is not dependent on soot formation, V is expected to be generally enriched within smaller HFO-PM particles from marine engines, enhancing its toxicity.

A high-flux upgrade for the BRISP spectrometer at ILL.

To date, the BRISP spectrometer represents the state-of-the-art for every instrument aiming to perform Brillouin neutron scattering. Exploiting accurate ray-tracing McStas simulations, we investigate an improved configuration of the BRISP primary spectrometer to provide a higher flux at the sample position, while preserving all the present capabilities of the instrument. This configuration is based on a neutron guide system and is designed to fit the instrument platform with no modifications of the secondary spectrometer. These evaluations show that this setup can achieve a flux gain factor ranging from 3 to 6, depending on the wavelength. This can expand the experimental possibilities of BRISP towards smaller samples, possibly using also complex sample environments.

Real-time observation of the isothermal crystallization kinetics in a deeply supercooled liquid.

Below the melting temperature Tm, crystals are the stable phase of typical elemental or molecular systems. However, cooling down a liquid below Tm, crystallization is anything but inevitable. The liquid can be supercooled, eventually forming a glass below the glass transition temperature Tg. Despite their long lifetimes and the presence of strong barriers that produces an apparent stability, supercooled liquids and glasses remain intrinsically a metastable state and thermodynamically unstable towards the crystal. Here we investigated the isothermal crystallization kinetics of the prototypical strong glassformer GeO2 in the deep supercooled liquid at 1100 K, about half-way between Tm and Tg. The crystallization process has been observed through time-resolved neutron diffraction for about three days. Data show a continuous reorganization of the amorphous structure towards the alpha-quartz phase with the final material composed by crystalline domains plunged into a low-density, residual amorphous matrix. A quantitative analysis of the diffraction patterns allows determining the time evolution of the relative fractions of crystal and amorphous, that was interpreted through an empirical model for the crystallization kinetics. This approach provides a very good description of the experimental data and identifies a predator-prey-like mechanism between crystal and amorphous, where the density variation acts as a blocking barrier.

Small-angle neutron scattering and molecular dynamics structural study of gelling DNA nanostars.

DNA oligomers with properly designed sequences self-assemble into well defined constructs. Here, we exploit this methodology to produce bulk quantities of tetravalent DNA nanostars (each one composed of 196 nucleotides) and to explore the structural signatures of their aggregation process. We report small-angle neutron scattering experiments focused on the evaluation of both the form factor and the temperature evolution of the scattered intensity at a nanostar concentration where the system forms a tetravalent equilibrium gel. We also perform molecular dynamics simulations of one isolated tetramer to evaluate the form factor numerically, without resorting to any approximate shape. The numerical form factor is found to be in very good agreement with the experimental one. Simulations predict an essentially temperature-independent form factor, offering the possibility to extract the effective structure factor and its evolution during the equilibrium gelation.

Collective ion dynamics in liquid zinc: evidence for complex dynamics in a non-free-electron liquid metal.

A detailed inelastic neutron scattering investigation of the THz dynamics of liquid zinc is presented. The observed Q dependence clearly reveals the existence of a complex dynamics made up of two distinct excitations. The highest energy mode is the prolongation of the longitudinal acoustic density fluctuations whereas the comparison with the phonon dynamics of crystalline hcp zinc suggests a transverse acousticlike nature for the second one. This mode seems related to peculiar anisotropic interactions, possibly connected to the behavior of the crystalline phase.

Revealing the fast atomic motion of network glasses.

Still very little is known on the relaxation dynamics of glasses at the microscopic level due to the lack of experiments and theories. It is commonly believed that glasses are in a dynamical arrested state, with relaxation times too large to be observed on human time scales. Here we provide the experimental evidence that glasses display fast atomic rearrangements within a few minutes, even in the deep glassy state. Following the evolution of the structural relaxation in a sodium silicate glass, we find that this fast dynamics is accompanied by the absence of any detectable aging, suggesting a decoupling of the relaxation time and the viscosity in the glass. The relaxation time is strongly affected by the network structure with a marked increase at the mesoscopic scale associated with the ion-conducting pathways. Our results modify the conception of the glassy state and asks for a new microscopic theory.

Structural evolution and medium range order in permanently densified vitreous SiO2.

Positron annihilation lifetime spectroscopy is employed to measure the size of the interstitial void spaces characterizing the structure of a set of permanently densified SiO2 glasses. The average volume of the voids is markedly affected by the densification process and linearly shrinks by almost an order of magnitude after a relative density variation of 22%. In addition, x-ray diffraction shows that this change of density does not modify appreciably the short range order, which remains organized in SiO4 tetrahedra. These results strongly suggest a porous medium description for v-SiO2 glasses where the compressibility and the medium range order are dominated by the density variation of the voids volume up to densities close to that of α-quartz.

Role of disorder in the thermodynamics and atomic dynamics of glasses.

We measured the density of vibrational states (DOS) and the specific heat of various glassy and crystalline polymorphs of SiO2. The typical (ambient) glass shows a well-known excess of specific heat relative to the typical crystal (α-quartz). This, however, holds when comparing a lower-density glass to a higher-density crystal. For glassy and crystalline polymorphs with matched densities, the DOS of the glass appears as the smoothed counterpart of the DOS of the corresponding crystal; it reveals the same number of the excess states relative to the Debye model, the same number of all states in the low-energy region, and it provides the same specific heat. This shows that glasses have higher specific heat than crystals not due to disorder, but because the typical glass has lower density than the typical crystal.

Terahertz Dynamics in Human Cells and Their Chromatin.

The terahertz dynamics of human cells of the U937 line and their chromatin has been investigated by high-resolution inelastic X-ray scattering. To highlight its dynamical features in situ, nuclear DNA has been stained by uranyl-acetate salt. The general behavior of the collective dynamics of the whole cell is quite similar to that of bulk water, with a nearly wavevector-independent branch located at about 5 meV and a propagating mode with a linear trend corresponding to a speed of sound of 2900 ± 100 m/s. We provide the first experimental evidence for the existence of two branches also in the dispersion curves of chromatin. The high-energy mode displays an acoustic-like behavior with a sound velocity similar to unstained cells, but in this case the branch likely originates from the superposition of intramolecular DNA optic modes. A low-energy optic-like branch, distinctive of the chromatin moiety, is found at about 2.5 meV.

Emergence of crystal-like atomic dynamics in glasses at the nanometer scale.

The vibrational dynamics of a permanently densified silica glass is compared to the one of an α-quartz polycrystal, the silica polymorph of the same density and local structure. The combined use of inelastic x-ray scattering experiments and ab initio numerical calculations provides compelling evidence of a transition, in the glass, from the isotropic elastic response at long wavelengths to a microscopic regime as the wavelength decreases below a characteristic length ξ of a few nanometers, corresponding to about 20 interatomic distances. In the microscopic regime the glass vibrations closely resemble those of the polycrystal, with excitations related to the acoustic and optic modes of the crystal. A coherent description of the experimental results is obtained assuming that the elastic modulus of the glass presents spatial heterogeneities of an average size a ~ ξ/2 π.

Nodular dermatofibrosis in a dog without a renal tumour or a mutation in the folliculin gene.

Canine nodular dermatofibrosis is a rare skin disease associated with renal cystadenoma or cystadenocarcinoma and uncommonly with uterine leiomyoma. It is generally seen in German shepherd dogs, but has been also reported in other breeds, and a relationship has been suggested with mutation of the gene encoding folliculin (FLCN), which is located on chromosome 5. A 10-year-old female golden retriever was presented because of numerous firm cutaneous nodules up to 4 cm in diameter over the entire body surface. Cytological and histopathological examinations confirmed generalized cutaneous nodular dermatofibrosis, but ultrasonography of both kidneys ruled out renal neoplasia. Ovariohysterectomy was performed because of prolonged oestrus periods. Microscopical examination of the excised tissues confirmed the absence of uterine neoplasia, but identified rete adenoma of the right ovary. Abdominal ultrasound performed repeatedly over a 5-year follow-up period did not identify any alteration in the renal parenchyma. Molecular studies excluded the presence of any mutation in the FLCN gene.

Debye to non-Debye scaling of the Boson peak dynamics: critical behavior and local disorder in vitreous germania.

We report on the observation of a significant softening of the Boson peak (BP) frequency of vitreous GeO(2) above the glass transition temperature. The softening reminds a critical trend, with a transition temperature intermediate between the glass transition temperature, T(g), and the melting point. The softening of the BP frequency corresponds to a transition from a region dominated by Debye scaling to a non-Debye one. Below T(g) the density of vibrational states varies according to the modification of the elastic continuum medium. Above T(g) the relevant softening of the BP modes can be explained by a broadening of the distribution of elastic constants between neighboring atoms, induced by the structural rearrangement. These findings are discussed together with recent experimental and theoretical results on the low frequency vibrations in glasses.

Histomorphometric analysis of glucocorticoid-induced osteoporosis.

Bone histomorphometry or quantitative histology consists of counting or measuring tissue components: cells, extracellular constituents and microarchitecture. Bone histomorphometry is the only method that allows the measurement of mineralization rate and the study of bone formation at three levels: cell, remodeling unit and tissue levels. It is a useful tool to explain the pathogenesis and cellular mechanisms of different metabolic bone diseases such as glucocorticoid-induced osteoporosis (GIO). Glucocorticoids (GC) affect calcium and bone metabolism at every level, but the main effect is the osteoblastic dysfunction. Concerning the bone formation, some histomorphometric studies have shown a depressed osteoblastic activity at a cell, bone remodeling unit, and tissue levels. In addition, there is evidence of a shortening of the period in which the osteoblasts work actively forming the bone matrix. This latter effect seems to occur after high cumulative doses of GC. With regard to the resorption, the results are still debated, but histomorphometric parameters seem to be increased in the majority of studies, at least in the first period of the GC treatment. From a structural point of view, GC seem to induce a thinning of the trabeculae without their perforation, which occurs only after high cumulative doses. Anti-resorptive treatments, such as bisphosphonates, are able to counteract the negative effects of GC on bone. In particular, along with their active working period, they prolong the lifespan of osteoblasts and osteocytes. In addition, the anti-resorptive treatments seem to extend the time for secondary mineralization through a reduction of the Activation Frequency. The latter is an intriguing mechanism of bisphosphonates in GIO that needs further ad hoc investigations.