Wave-Vector Dependence of the Dynamics in Supercooled Metallic Liquids.

We present a detailed investigation of the wave-vector dependence of collective atomic motion in Au_{49}Cu_{26.9}Si_{16.3}Ag_{5.5}Pd_{2.3} and Pd_{42.5}Cu_{27}Ni_{9.5}P_{21} supercooled liquids close to the glass transition temperature. Using x-ray photon correlation spectroscopy in a previously uncovered spatial range of only a few interatomic distances, we show that the microscopic structural relaxation process mimics the structure and presents a marked slowing down at the main average interparticle distance. This behavior is accompanied by dramatic changes in the shape of the intermediate scattering functions, which suggest the presence of large dynamical heterogeneities at length scales corresponding to a few particle diameters. A ballisticlike mechanism of particle motion seems to govern the structural relaxation of the two systems in the highly viscous phase, likely associated with hopping of caged particles in agreement with theoretical studies.

Tumour parcellation and quantification (TuPaQ): a tool for refining biomarker analysis through rapid and automated segmentation of tumour epithelium.

BACKGROUND AND AIMS: Immunohistochemistry (IHC) is an essential component of biomarker research in cancer. Automated biomarker quantification is hampered by the failure of computational algorithms to discriminate 'negative' tumour cells from 'negative' stromal cells. We sought to develop an algorithm for segmentation of tumour epithelium in colorectal cancer (CRC), irrespective of the biomarker expression in the cells. METHODS AND RESULTS: We developed tumour parcellation and quantification (TuPaQ) to segment tumour epithelium and parcellate sections into 'epithelium' and 'non-epithelium'. TuPaQ comprises image pre-processing, extraction of regions of interest (ROIs) and quantification of tumour epithelium (total area occupied by epithelium and number of nuclei in the occupied area). A total of 286 TMA cores from CRC were manually annotated and analysed using the commercial halo software to provide ground truth. The performance of TuPaQ was evaluated against the ground truth using a variety of metrics. The image size of each core was 7000 × 7000 pixels and each core was analysed in a matter of seconds. Pixel × pixel analysis showed a sensitivity of 84% and specificity of 95% in detecting epithelium. The mean tumour area obtained by TuPaQ was very close to the area quantified after manual annotation (r = 0.956, P < 0.001). Moreover, quantification of tumour nuclei by TuPaQ correlated very strongly with that of halo (r = 0.891, P < 0.001). CONCLUSION: TuPaQ is a very rapid and accurate method of separating the epithelial and stromal compartments of colorectal tumours. This will allow more accurate and objective analysis of immunohistochemistry.

Relaxation Decoupling in Metallic Glasses at Low Temperatures.

Upon cooling, glass-forming liquids experience a dynamic decoupling in the fast ß and slow α process, which has greatly influenced glass physics. By exploring an extremely wide temporal and temperature range, we find a surprising gradual change of the relaxation profile from a single-step to a two-step decay upon cooling in various metallic glasses. This behavior implies a decoupling of the relaxation in two different processes in a glass state: a faster one likely related to the anomalous stress-dominated microscopic dynamics, and a slower one associated with subdiffusive motion at larger scales with a broader distribution of relaxation times.

Anharmonic damping of terahertz acoustic waves in a network glass and its effect on the density of vibrational states.

We report the observation, by means of high-resolution inelastic x-ray scattering, of an unusually large temperature dependence of the sound attenuation of a network glass at terahertz frequency, an unprecedentedly observed phenomenon. The anharmonicity can be ascribed to the interaction between the propagating acoustic wave and the bath of thermal vibrations. At low temperatures the sound attenuation follows a Rayleigh-Gans scattering law. As the temperature is increased the anharmonic process sets in, resulting in an almost quadratic frequency dependence of the damping in the entire frequency range. We show that the temperature variation of the sound damping accounts quantitatively for the temperature dependence of the density of vibrational states.

Silica nanoparticles as tracers of the gelation dynamics of a natural biopolymer physical gel.

The gelation of methylcellulose in water has been studied by X-ray photon correlation spectroscopy, electrophoresis and rheological measurements by looking into the dynamics of silica nanoparticles as tracers in the polymer matrix. The temperature and scattering vector dependence of the structural relaxation time is investigated at the nanometric length scale during the formation of the strong gel state. We find a stress-dominated dynamics on approaching the gel state, characterized by a hyper-diffusive motion of the silica particles. These results support the idea of a unifying scenario for the dynamics of complex out of equilibrium soft materials.

An ER-resident membrane protein complex regulates nicotinic acetylcholine receptor subunit composition at the synapse.

Nicotinic acetylcholine receptors (nAChRs) are homo- or heteropentameric ligand-gated ion channels mediating excitatory neurotransmission and muscle activation. Regulation of nAChR subunit assembly and transfer of correctly assembled pentamers to the cell surface is only partially understood. Here, we characterize an ER transmembrane (TM) protein complex that influences nAChR cell-surface expression and functional properties in Caenorhabditis elegans muscle. Loss of either type I TM protein, NRA-2 or NRA-4 (nicotinic receptor associated), affects two different types of muscle nAChRs and causes in vivo resistance to cholinergic agonists. Sensitivity to subtype-specific agonists of these nAChRs is altered differently, as demonstrated by whole-cell voltage-clamp of dissected adult muscle, when applying exogenous agonists or after photo-evoked, channelrhodopsin-2 (ChR2) mediated acetylcholine (ACh) release, as well as in single-channel recordings in cultured embryonic muscle. These data suggest that nAChRs desensitize faster in nra-2 mutants. Cell-surface expression of different subunits of the 'levamisole-sensitive' nAChR (L-AChR) is differentially affected in the absence of NRA-2 or NRA-4, suggesting that they control nAChR subunit composition or allow only certain receptor assemblies to leave the ER.

Compressed correlation functions and fast aging dynamics in metallic glasses.

We present x-ray photon correlation spectroscopy measurements of the atomic dynamics in a Zr(67)Ni(33) metallic glass, well below its glass transition temperature. We find that the decay of the density fluctuations can be well described by compressed, thus faster than exponential, correlation functions which can be modeled by the well-known Kohlrausch-Williams-Watts function with a shape exponent ß larger than one. This parameter is furthermore found to be independent of both waiting time and wave-vector, leading to the possibility to rescale all the correlation functions to a single master curve. The dynamics in the glassy state is additionally characterized by different aging regimes which persist in the deep glassy state. These features seem to be universal in metallic glasses and suggest a nondiffusive nature of the dynamics. This universality is supported by the possibility of describing the fast increase of the structural relaxation time with waiting time using a unique model function, independently of the microscopic details of the system.

Atomic-scale relaxation dynamics and aging in a metallic glass probed by x-ray photon correlation spectroscopy.

We use x-ray photon correlation spectroscopy to investigate the structural relaxation process in a metallic glass on the atomic length scale. We report evidence for a dynamical crossover between the supercooled liquid phase and the metastable glassy state, suggesting different origins of the relaxation process across the transition. Furthermore, using different cooling rates, we observe a complex hierarchy of dynamic processes characterized by distinct aging regimes. Strong analogies with the aging dynamics of soft glassy materials, such as gels and concentrated colloidal suspensions, point at stress relaxation as a universal mechanism driving the relaxation dynamics of out-of-equilibrium systems.

Acoustic excitations in glassy sorbitol and their relation with the fragility and the boson peak.

We report a detailed analysis of the dynamic structure factor of glassy sorbitol by using inelastic X-ray scattering and previously measured light scattering data [B. Ruta, G. Monaco, F. Scarponi, and D. Fioretto, Philos. Mag. 88, 3939 (2008)]. The thus obtained knowledge on the density-density fluctuations at both the mesoscopic and macroscopic length scale has been used to address two debated topics concerning the vibrational properties of glasses. The relation between the acoustic modes and the universal boson peak (BP) appearing in the vibrational density of states of glasses has been investigated, also in relation with some recent theoretical models. Moreover, the connection between the elastic properties of glasses and the slowing down of the structural relaxation process in supercooled liquids has been scrutinized. For what concerns the first issue, it is here shown that the wave vector dependence of the acoustic excitations can be used, in sorbitol, to quantitatively reproduce the shape of the boson peak, supporting the relation between BP and acoustic modes. For what concerns the second issue, a proper study of elasticity over a wide spatial range is shown to be fundamental in order to investigate the relation between elastic properties and the slowing down of the dynamics in the corresponding supercooled liquid phase.

Sound attenuation at terahertz frequencies and the boson peak of vitreous silica.

The propagation and damping of the acoustic excitations in vitreous silica is measured at terahertz frequencies using inelastic x-ray scattering. The apparent sound velocity shows a marked dispersion with frequency while the sound attenuation undergoes a crossover from a fourth to a second power law frequency dependence. This finding solves a recent controversy concerning the location of this crossover in vitreous silica, clarifying that it occurs at the position of the glass-characteristic excess of vibrational modes known as boson peak, and thus establishing a direct connection between boson peak and acoustic dispersion curves.

Communication: High-frequency acoustic excitations and boson peak in glasses: A study of their temperature dependence.

The results of a combined experimental study of the high-frequency acoustic dynamics and of the vibrational density of states (VDOS) as a function of temperature in a glass of sorbitol are reported here. The excess in the VDOS at approximately 4.5 meV over the Debye, elastic continuum prediction (boson peak) is found to be clearly related to anomalies observed in the acoustic dispersion curve in the mesoscopic wavenumber range of few nm(-1). The quasiharmonic temperature dependence of the acoustic dispersion curves offers a natural explanation for the observed scaling of the boson peak with the elastic medium properties.

Ultrastable metallic glasses formed on cold substrates.

Vitrification from physical vapor deposition is known to be an efficient way for tuning the kinetic and thermodynamic stability of glasses and significantly improve their properties. There is a general consensus that preparing stable glasses requires the use of high substrate temperatures close to the glass transition one, Tg. Here, we challenge this empirical rule by showing the formation of Zr-based ultrastable metallic glasses (MGs) at room temperature, i.e., with a substrate temperature of only 0.43Tg. By carefully controlling the deposition rate, we can improve the stability of the obtained glasses to higher values. In contrast to conventional quenched glasses, the ultrastable MGs exhibit a large increase of Tg of ∼60 K, stronger resistance against crystallization, and more homogeneous structure with less order at longer distances. Our study circumvents the limitation of substrate temperature for developing ultrastable glasses, and provides deeper insight into glasses stability and their surface dynamics.

Relaxation processes and physical aging in metallic glasses.

Since their discovery in the 1960s, metallic glasses have continuously attracted much interest across the physics and materials science communities. In the forefront are their unique properties, which hold the alluring promise of broad application in fields as diverse as medicine, environmental science and engineering. However, a major obstacle to their wide-spread commercial use is their inherent temporal instability arising from underlying relaxation processes that can dramatically alter their physical properties. The result is a physical aging process which can bring about degradation of mechanical properties, namely through embrittlement and catastrophic mechanical failure. Understanding and controlling the effects of aging will play a decisive role in our on-going endeavor to advance the use of metallic glasses as structural materials, as well as in the more general comprehension of out-of-equilibrium dynamics in complex systems. This review presents an overview of the current state of the art in the experimental advances probing physical aging and relaxation processes in metallic glasses. Similarities and differences between other hard and soft matter glasses are highlighted. The topic is discussed in a multiscale approach, first presenting the key features obtained in macroscopic studies, then connecting them to recent novel microscopic investigations. Particular emphasis is put on the occurrence of distinct relaxation processes beyond the main structural process in viscous metallic melts and their fate upon entering the glassy state, trying to disentangle results and formalisms employed by the different groups of the glass-science community. A microscopic viewpoint is presented, in which physical aging manifests itself in irreversible atomic-scale processes such as avalanches and intermittent dynamics, ascribed to the existence of a plethora of metastable glassy states across a complex energy landscape. Future experimental challenges and the comparison with recent theoretical and numerical simulations are discussed as well.

Hard X-rays as pump and probe of atomic motion in oxide glasses.

Nowadays powerful X-ray sources like synchrotrons and free-electron lasers are considered as ultimate tools for probing microscopic properties in materials. However, the correct interpretation of such experiments requires a good understanding on how the beam affects the properties of the sample, knowledge that is currently lacking for intense X-rays. Here we use X-ray photon correlation spectroscopy to probe static and dynamic properties of oxide and metallic glasses. We find that although the structure does not depend on the flux, strong fluxes do induce a non-trivial microscopic motion in oxide glasses, whereas no such dependence is found for metallic glasses. These results show that high fluxes can alter dynamical properties in hard materials, an effect that needs to be considered in the analysis of X-ray data but which also gives novel possibilities to study materials properties since the beam can not only be used to probe the dynamics but also to pump it.

Geomorphic response to sea level and climate changes during Late Quaternary in a humid tropical coastline: Terrain evolution model from Southwest India.

The coastal lands of southern Kerala, SW India in the vicinity of Achankovil and Thenmala Shear Zones reveal a unique set of geomorphic features like beach ridges, runnels, chain of wetlands, lakes, estuaries, etc. The chain of wetlands and water bodies that are seen in the eastern periphery of the coastal lands indicates the remnants of the upper drainage channels of the previously existed coastal plain rivers of Late Pleistocene age that are later broadened due to coastal erosion under the transgressive phase. The terrain evolutionary model developed from the results of the study shows that the Late Pleistocene transgressive events might have carved out a major portion of the land areas drained by the coastal plain rivers and as a result the coastal cliff has been retreated several kilometers landwards. The NNE-SSW trending beach ridges located close to the inland wetlands indicate the extent of shoreline shift towards eastwards during Late Pleistocene period. The present beach parallel ridges in the younger coastal plain indicate the limit of the Mid Holocene shoreline as the transgression was not so severe compared to Late Pleistocene event. The zone of convergence of the two sets of beach ridges coincides with the areas of economically viable heavy mineral placers that resulted from the size and density based sorting under the repeated transgressive events to which the coast had subjected to. The chain of wetlands in the eastern side of the study area has been evolved from a mega lagoon existed during Late Pleistocene. The Pallikkal River that links discrete eastern wetland bodies has been evolved into its present form during Early Holocene.

Perinatal and early childhood outcomes of twins versus triplets.

The purpose of this prospective cohort study of twins and triplets was to evaluate perinatal and early childhood outcomes through 18 months of age. The study population included 141 twin pregnancies (282 twin children) and 8 triplet pregnancies (24 triplet children) recruited between May, 1996 and June, 2001. Mothers of triplets versus twins were significantly more likely to have infertility treatments, to be overweight or obese before conception, to be admitted antenatally, and to deliver by cesarean section. Length of gestation for triplets was significantly shorter (-2.31 weeks, p < .0001), and more likely to be less than 35 weeks (Adjusted Odds Ratio [AOR] 9.38, 95% confidence interval [CI] 3.22-27.29). Average birthweight for triplets was significantly lighter (-495 grams, p < .0001), and more likely to be low birthweight (AOR 11.38, 95% CI 3.11-41.61). Triplets were also more likely to be admitted to neonatal intensive care (AOR 7.97, 95% CI 2.13-29.77), to require mechanical ventilation (AOR 5.67, 95% CI 2.05-15.65), to develop respiratory distress syndrome (AOR 12.50, 95% CI 3.89-40.20), or a major morbidity (retinopathy of prematurity, necrotizing enterocolitis, ventilator support, or grade III or IV intraventricular hemorrhage, AOR 5.67, 95% CI 2.05-15.65). Weight, length, and head circumference was significantly smaller at birth for triplets compared to twins, and these differences remained through 18 months of age, along with lower mental developmental scores at the oldest age. Compared to twins, triplets have greater neonatal morbidity, and through 18 months of age lower mental and motor scores, slower postnatal growth and more residual stunting, particularly of length and head circumference.

Unveiling the structural arrangements responsible for the atomic dynamics in metallic glasses during physical aging.

Understanding and controlling physical aging, that is, the spontaneous temporal evolution of out-of-equilibrium systems, represents one of the greatest tasks in material science. Recent studies have revealed the existence of a complex atomic motion in metallic glasses, with different aging regimes in contrast with the typical continuous aging observed in macroscopic quantities. By combining dynamical and structural synchrotron techniques, here for the first time we directly connect previously identified microscopic structural mechanisms with the peculiar atomic motion, providing a broader unique view of their complexity. We show that the atomic scale is dominated by the interplay between two processes: rearrangements releasing residual stresses related to a cascade mechanism of relaxation, and medium range ordering processes, which do not affect the local density, likely due to localized relaxations of liquid-like regions. As temperature increases, a surprising additional secondary relaxation process sets in, together with a faster medium range ordering, likely precursors of crystallization.

Tropical Peat and Peatland Development in the Floodplains of the Greater Pamba Basin, South-Western India during the Holocene.

Holocene sequences in the humid tropical region of Kerala, South-western (SW) India have preserved abundance of organic-rich sediments in the form of peat and its rapid development in a narrow time frame towards Middle Holocene has been found to be significant. The sub-coastal areas and flood plains of the Greater Pamba Basin have provided palaeorecords of peat indicating that the deposits are essentially formed within freshwater. The combination of factors like stabilized sea level and its subsequent fall since the Middle Holocene, topographic relief and climatic conditions led to rapid peat accumulation across the coastal lowlands. The high rainfall and massive floods coupled with a rising sea level must have inundated > 75% of the coastal plain land converting it into a veritable lagoon-lake system that eventually led to abrupt termination of the forest ecosystem and also converted the floodplains into peatland where accumulation of peat almost to 2.0-3.0 m thickness in coastal lowlands and river basins during the shorter interval in the Middle Holocene. Vast areas of the coastal plains of Kerala have been converted into carbon rich peatland during the Middle Holocene and transforming the entire coastal stretch and associated landforms as one of the relatively youngest peatlands in the extreme southern tip of India. Unlike the uninterrupted formation of peatlands of considerable extent during the Holocene in Southeast Asia, the south Peninsular Indian region has restricted and short intervals of peatlands in the floodplains and coastal lowlands. Such a scenario is attributed to the topographic relief of the terrain and the prevailing hydrological regimes and environmental conditions as a consequence of monsoon variability since Middle Holocene in SW India. Considering the tropical coastal lowlands and associated peatlands are excellent repositories of carbon, they are very important for regional carbon cycling and habitat diversity. The alarming rate of land modification and development is destabilizing these carbon pools resulting in large scale carbon emissions to the atmosphere and loss of low-latitude peat palaeorecords. Therefore, these palaeorecords are to be conserved and addressed for better understanding and utilizing the carbon pool for effective climate change adaptation. This communication is the first attempt of addressing the peat formation and peatland development during the Holocene from the tropical region of Peninsular India.

The Hispanic paradox in twin pregnancies.

The objective of this study was to compare length of gestation, fetal growth, and birthweight by race/ethnicity and pregravid weight groups in twin pregnancies. Three thousand and thirty-six twin pregnancies of 28 weeks or more gestation were divided by race/ethnicity (White, Black and Hispanic), and pregravid body mass index (BMI) groups (less than 25.0 vs. 25.0 or more). Outcomes were modeled using multiple regression, controlling for confounders, with White non-Hispanic women as the reference group. Hispanic women had the highest average birthweight and the longest gestation, as well as the lowest proportions of low birthweight, very low birthweight, preterm and early preterm births of the 3 race/ethnicity groups. In the multivariate analyses, Hispanic women had significantly longer gestations (by 7.8 days) and faster rates of fetal growth midgestation (20 to 28 weeks, by 17.4 g/week) and late gestation (after 28 weeks, by 5.3 g/week), whereas Black women had significantly slower rates of fetal growth (by 5.7 g/week and by 4.5 g/week, respectively). These findings in twins reflect the racial and ethnic disparities previously shown in singletons, including the Hispanic paradox of longer gestations and higher rates of fetal growth.

Elevated maternal glucose concentrations and placental infection in twin pregnancies.

OBJECTIVE: To evaluate the association between maternal screening glucose concentration and placental infection in nondiabetic twin pregnancies. STUDY DESIGN: One thousand sixty-one nondiabetic twin pregnancies at > or =28 weeks' gestation were divided into 3 groups based on the screening 50-g fasting glucose concentration at 24-28 weeks: lowest quartile (< 96 mg/dL), middle 2 quartiles (96-128 mg/dL) and upper quartile (> 128 mg/dL). Outcomes were modeled using general linear and multinomial logistic regression, controlling for confounding factors. RESULTS: The middle and highest glucose groups were associated with increased risks for clinical chorioamnionitis (adjusted OR [AOR] 3.18, 95% CI 1.34, 7.54; AOR 6.80, CI 1.89, 24.53, respectively). Birth at <32 weeks and histologic diagnosis of placental infection (chorioamnionitis, funisitis, necrosis, vasculitis or villitis) were significantly associated only with the highest glucose group (AOR 1.79, CI 1.02, 3.13; AOR 6.95, CI 1.10, 8.68, respectively). CONCLUSION: Elevated screening glucose in nondiabetic twin pregnancies may be a marker of placental inflammation and infection.