10,440 research outputs found
Two-dimensional NMR lineshape analysis of single, multiple, zero and double quantum correlation experiments
NMR spectroscopy provides a powerful approach for the characterisation of chemical exchange and molecular interactions by analysis of series of experiments acquired over the course of a titration measurement. The appearance of NMR resonances undergoing chemical exchange depends on the frequency difference relative to the rate of exchange, and in the case of one-dimensional experiments chemical exchange regimes are well established and well known. However, two-dimensional experiments present additional complexity, as at least one additional frequency difference must be considered. Here we provide a systematic classification of chemical exchange regimes in two-dimensional NMR spectra. We highlight important differences between exchange in HSQC and HMQC experiments, that on a practical level result in more severe exchange broadening in HMQC spectra, but show that complementary alternatives to the HMQC are available in the form of HZQC and HDQC experiments. We present the longitudinal relaxation optimised SOFAST-H(Z/D)QC experiment for the simultaneous acquisition of sensitivity-enhanced HZQC and HDQC spectra, and the longitudinal and transverse relaxation optimised BEST-ZQ-TROSY for analysis of large molecular weight systems. We describe the application of these experiments to the characterisation of the interaction between the Hsp90 N-terminal domain and a small molecule ligand, and show that the independent analysis of HSQC, HMQC, HZQC and HDQC experiments provides improved confidence in the fitted dissociation constant and dissociation rate. Joint analysis of such data may provide improved sensitivity to detect and analyse more complex multi-state interaction mechanisms such as induced fit or conformational selection
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Highlights of OH, H2SO4, and methane sulfonic acid measurements made aboard the NASA P-3B during Transport and Chemical Evolution over the Pacific
Measurements of hydroxyl radical (OH), sulfuric acid (H2SO4), and methane sulfonic acid (MSA) were performed aboard the NASA P-3B using the selected ion chemical ionization mass spectrometry technique during the Transport and Chemical Evolution over the Pacific (TRACE-P) study. Photochemical box model calculations of OH concentrations yielded generally good agreement with an overall tendency to overestimate the measured OH by ∼20%. Further analysis reveals that this overestimation is present only at altitudes greater than ∼1.5 km, with the model underestimating OH measurements at lower altitudes. Boundary layer H2SO4 measurements, performed in a volcanic plume off the southern coast of Japan, revealed some of the largest marine boundary layer H2SO4 concentrations ever observed and were accompanied by new particle formation. Nighttime measurements of OH, H2SO4, and MSA in the remote pacific off Midway Island revealed significant boundary layer concentrations of H2SO4 and MSA, indicating evidence of nighttime boundary layer oxidation processes but in the absence of OH. A cursory exploration of the sources of production of the H2SO4 and MSA observed at night is presented
Modeling Fibrillogenesis of Collagen-Mimetic Molecules
One of the most robust examples of self-assembly in living organisms is the formation of collagen architectures. Collagen type I molecules are a crucial component of the extracellular matrix, where they self-assemble into fibrils of well-defined axial striped patterns. This striped fibrillar pattern is preserved across the animal kingdom and is important for the determination of cell phenotype, cell adhesion, and tissue regulation and signaling. The understanding of the physical processes that determine such a robust morphology of self-assembled collagen fibrils is currently almost completely missing. Here, we develop a minimal coarse-grained computational model to identify the physical principles of the assembly of collagen-mimetic molecules. We find that screened electrostatic interactions can drive the formation of collagen-like filaments of well-defined striped morphologies. The fibril axial pattern is determined solely by the distribution of charges on the molecule and is robust to the changes in protein concentration, monomer rigidity, and environmental conditions. We show that the striped fibrillar pattern cannot be easily predicted from the interactions between two monomers but is an emergent result of multibody interactions. Our results can help address collagen remodeling in diseases and aging and guide the design of collagen scaffolds for biotechnological applications
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Some attributes of a language for property-based testing.
Property-based testing is a testing technique that evaluates executions of a program. The method checks that specifications, called properties, hold throughout the execution of the program. TASpec is a language used to specify these properties. This paper compares some attributes of the language with the specification patterns used for model-checking languages, and then presents some descriptions of properties that can be used to detect common security flaws in programs. This report describes the results of a one year research project at the University of California, Davis, which was funded by a University Collaboration LDRD entitled ''Property-based Testing for Cyber Security Assurance''
Irish Ice Sheet dynamics during deglaciation of the central Irish Midlands: Evidence of ice streaming and surging from airborne LiDAR
High resolution digital terrain models (DTMs) generated from airborne LiDAR data and supplemented by field evidence are used to map glacial landform assemblages dating from the last glaciation (Midlandian glaciation; OI stages 2-3) in the central Irish Midlands. The DTMs reveal previously unrecognised low-amplitude landforms, including crevasse-squeeze ridges and mega-scale glacial lineations overprinted by conduit fills leading to ice-marginal subaqueous deposits. We interpret this landform assemblage as evidence for surging behaviour during ice recession. The data indicate that two separate phases of accelerated ice flow were followed by ice sheet stagnation during overall deglaciation. The second surge event was followed by a subglacial outburst flood, forming an intricate esker and crevasse-fill network. The data provide the first clear evidence that ice flow direction was eastward along the eastern watershed of the Shannon River basin, at odds with previous models, and raise the possibility that an ice stream existed in this area. Our work demonstrates the potential for airborne LiDAR surveys to produce detailed paleoglaciological reconstructions and to enhance our understanding of complex palaeo ice sheet dynamics
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Flatback airfoil wind tunnel experiment.
A computational fluid dynamics study of thick wind turbine section shapes in the test section of the UC Davis wind tunnel at a chord Reynolds number of one million is presented. The goals of this study are to validate standard wind tunnel wall corrections for high solid blockage conditions and to reaffirm the favorable effect of a blunt trailing edge or flatback on the performance characteristics of a representative thick airfoil shape prior to building the wind tunnel models and conducting the experiment. The numerical simulations prove the standard wind tunnel corrections to be largely valid for the proposed test of 40% maximum thickness to chord ratio airfoils at a solid blockage ratio of 10%. Comparison of the computed lift characteristics of a sharp trailing edge baseline airfoil and derived flatback airfoils reaffirms the earlier observed trend of reduced sensitivity to surface contamination with increasing trailing edge thickness
Retrograde semaphorin-plexin signalling drives homeostatic synaptic plasticity.
Homeostatic signalling systems ensure stable but flexible neural activity and animal behaviour. Presynaptic homeostatic plasticity is a conserved form of neuronal homeostatic signalling that is observed in organisms ranging from Drosophila to human. Defining the underlying molecular mechanisms of neuronal homeostatic signalling will be essential in order to establish clear connections to the causes and progression of neurological disease. During neural development, semaphorin-plexin signalling instructs axon guidance and neuronal morphogenesis. However, semaphorins and plexins are also expressed in the adult brain. Here we show that semaphorin 2b (Sema2b) is a target-derived signal that acts upon presynaptic plexin B (PlexB) receptors to mediate the retrograde, homeostatic control of presynaptic neurotransmitter release at the neuromuscular junction in Drosophila. Further, we show that Sema2b-PlexB signalling regulates presynaptic homeostatic plasticity through the cytoplasmic protein Mical and the oxoreductase-dependent control of presynaptic actin. We propose that semaphorin-plexin signalling is an essential platform for the stabilization of synaptic transmission throughout the developing and mature nervous system. These findings may be relevant to the aetiology and treatment of diverse neurological and psychiatric diseases that are characterized by altered or inappropriate neural function and behaviour
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