443 research outputs found
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Ultrafast X-ray Science at the Sub-Picosecond Pulse Source
The ultrafast, high brightness x-ray free electron laser (XFEL) sources of the future have the potential to revolutionize the study of time dependent phenomena in the natural sciences. These linear accelerator (linac) sources will generate femtosecond (fs) x-ray pulses with peak flux comparable to conventional lasers, and far exceeding all other x-ray sources. The Stanford Linear Accelerator Center (SLAC) has pioneered the development of linac science and technology for decades, and since 2000 SLAC and the Stanford Synchrotron Radiation Laboratory (SSRL) have focused on the development of linac based ultrafast electron and x-ray sources. This development effort has led to the creation of a new x-ray source, called the Sub-Picosecond Pulse Source (SPPS), which became operational in 2003 [1]. The SPPS represents the first step toward the world's first hard x-ray free electron laser (XFEL), the Linac Coherent Light Source (LCLS), due to begin operation at SLAC in 2009. The SPPS relies on the same linac-based acceleration and electron bunch compression schemes that will be used at the LCLS to generate ultrashort, ultrahigh peak brightness electron bunches [2]. This involves creating an energy chirp on the electron bunch during acceleration and subsequent compression of the bunch in a series of energy-dispersive magnetic chicanes to create 80 fs electron pulses. The SPPS has provided an excellent opportunity to demonstrate the viability of these electron bunch compression schemes and to pursue goals relevant to the utilization and validation of XFEL light sources
Glucose-lactate metabolic cooperation in cancer: insights from a spatial mathematical model and implications for targeted therapy
A recent study has hypothesised a glucose–lactate metabolic symbiosis between adjacent hypoxic and oxygenated regions of a developing tumour, and proposed a treatment strategy to target this symbiosis. However, in vivo experimental support remains inconclusive. Here we develop a minimal spatial mathematical model of glucose–lactate metabolism to examine, in principle, whether metabolic symbiosis is plausible in human tumours, and to assess the potential impact of inhibiting it. We find that symbiosis is a robust feature of our model system—although on the length scale at which oxygen supply is diffusion-limited, its occurrence requires very high cellular metabolic activity—and that necrosis in the tumour core is reduced in the presence of symbiosis. Upon simulating therapeutic inhibition of lactate uptake, we predict that targeted treatment increases the extent of tissue oxygenation without increasing core necrosis. The oxygenation effect is correlated strongly with the extent of wild-type hypoxia and only weakly with wild-type symbiotic behaviour, and therefore may be promising for radiosensitisation of hypoxic, lactate-consuming tumours even if they do not exhibit a spatially well-defined symbiosis. Finally, we conduct in vitro experiments on the U87 glioblastoma cell line to facilitate preliminary speculation as to where highly malignant tumours might fall in our parameter space, and find that these experiments suggest a weakly symbiotic regime for U87 cells, thus raising the new question of what relationship might exist between symbiosis and tumour malignancy
Wearable wireless inertial measurement for sports applications
The advent of MEMS inertial sensors has reduced the size, cost and power requirements of 6 Degrees-of-Freedom inertial measurement systems to a level where their use can be considered for wearable wireless monitoring devices. Many applications for such Wearable Wireless Inertial Measurement Units exist in the area of sports and sports science. Such a system would be critical in providing data for the analysis of the kinematic motion data of an athlete - to characterise a player’s technique or track progress and provide accurate,
quantitative feedback to player and coach in near real time. A small, lightweight and low power device with the ability to sense the full range of human motion at a high sampling rate is required for such applications. It must also be robust, well sealed and comfortable to wear. Further development and miniaturisation of such devices coupled with progress in
energy scavenging may lead to their use in other areas and their near ubiquity, with the potential to be embedded within clothes, buildings, materials, objects and people for health monitoring, location tracking and other purpose
L-Edge Spectroscopy of Dilute, Radiation-Sensitive Systems Using a Transition-Edge-Sensor Array
We present X-ray absorption spectroscopy and resonant inelastic X-ray
scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous
ferricyanide. These measurements demonstrate the ability of high-throughput
transition-edge-sensor (TES) spectrometers to access the rich soft X-ray
(100-2000eV) spectroscopy regime for dilute and radiation-sensitive samples.
Our low-concentration data are in agreement with high-concentration
measurements recorded by conventional grating-based spectrometers. These
results show that soft X-ray RIXS spectroscopy acquired by high-throughput TES
spectrometers can be used to study the local electronic structure of dilute
metal-centered complexes relevant to biology, chemistry and catalysis. In
particular, TES spectrometers have a unique ability to characterize frozen
solutions of radiation- and temperature-sensitive samples.Comment: 19 pages, 4 figure
Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy
The multifunctional protein cytochrome c (cyt c) plays key roles in electron transport and apoptosis, switching function by modulating bonding between a heme iron and the sulfur in a methionine residue. This Fe-S(Met) bond is too weak to persist in the absence of protein constraints. We ruptured the bond in ferrous cyt c using an optical laser pulse and monitored the bond reformation within the protein active site using ultrafast x-ray pulses from an x-ray free-electron laser, determining that the Fe-S(Met) bond enthalpy is ~4 kcal/mol stronger than in the absence of protein constraints. The 4 kcal/mol is comparable with calculations of stabilization effects in other systems, demonstrating how biological systems use an entatic state for modest yet accessible energetics to modulate chemical function
Anisotropy enhanced X-ray scattering from solvated transition metal complexes
Time-resolved X-ray scattering patterns from photoexcited molecules in
solution are in many cases anisotropic at the ultrafast time scales accessible
at X-ray Free Electron Lasers (XFELs). This anisotropy arises from the
interaction of a linearly polarized UV-vis pump laser pulse with the sample,
which induces anisotropic structural changes that can be captured by
femtosecond X-ray pulses. In this work we describe a method for quantitative
analysis of the anisotropic scattering signal arising from an ensemble of
molecules and we demonstrate how its use can enhance the structural sensitivity
of the time-resolved X-ray scattering experiment. We apply this method on
time-resolved X-ray scattering patterns measured upon photoexcitation of a
solvated di-platinum complex at an XFEL and explore the key parameters
involved. We show that a combined analysis of the anisotropic and isotropic
difference scattering signals in this experiment allows a more precise
determination of the main photoinduced structural change in the solute, i.e.
the change in Pt-Pt bond length, and yields more information on the excitation
channels than the analysis of the isotropic scattering only. Finally, we
discuss how the anisotropic transient response of the solvent can enable the
determination of key experimental parameters such as the Instrument Response
Function.Comment: Accepted for publication in Journal of Synchrotron Radiatio
Atomistic characterization of the active-site solvation dynamics of a model photocatalyst
The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2 (dimen) 4 ] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution function, enabling the solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis
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