18,763 research outputs found
Topoisomer Differentiation of Molecular Knots by FTICR MS: Lessons from Class II Lasso Peptides
Lasso peptides constitute a class of bioactive peptides sharing a knotted
structure where the C-terminal tail of the peptide is threaded through and
trapped within an N-terminalmacrolactamring. The structural characterization of
lasso structures and differentiation from their unthreaded topoisomers is not
trivial and generally requires the use of complementary biochemical and
spectroscopic methods. Here we investigated two antimicrobial peptides
belonging to the class II lasso peptide family and their corresponding
unthreaded topoisomers: microcin J25 (MccJ25), which is known to yield
two-peptide product ions specific of the lasso structure under collisioninduced
dissociation (CID), and capistruin, for which CID does not permit to
unambiguously assign the lasso structure. The two pairs of topoisomers were
analyzed by electrospray ionization Fourier transform ion cyclotron resonance
mass spectrometry (ESI-FTICR MS) upon CID, infrared multiple photon
dissociation (IRMPD), and electron capture dissociation (ECD). CID and
ECDspectra clearly permitted to differentiate MccJ25 from its non-lasso
topoisomer MccJ25-Icm, while for capistruin, only ECD was informative and
showed different extent of hydrogen migration (formation of c\bullet/z from
c/z\bullet) for the threaded and unthreaded topoisomers. The ECD spectra of the
triply-charged MccJ25 and MccJ25-lcm showed a series of radical b-type product
ions {\eth}b0In{\TH}. We proposed that these ions are specific of
cyclic-branched peptides and result from a dual c/z\bullet and y/b
dissociation, in the ring and in the tail, respectively. This work shows the
potentiality of ECD for structural characterization of peptide topoisomers, as
well as the effect of conformation on hydrogen migration subsequent to electron
capture
Cumulate causes for the low contents of sulfide-loving elements in the continental crust
Despite the economic importance of chalcophile (sulfide-loving) and siderophile (metal-loving) elements (CSEs), it is unclear how they become enriched or depleted in the continental crust, compared with the oceanic crust. This is due in part to our limited understanding of the partitioning behaviour of the CSEs. Here I compile compositional data for mid-ocean ridge basalts and subduction-related volcanic rocks. I show that the mantle-derived melts that contribute to oceanic and continental crust formation rarely avoid sulfide saturation during cooling in the crust and, on average, subduction-zone magmas fractionate sulfide at the base of the continental crust prior to ascent. Differentiation of mantle-derived melts enriches lower crustal sulfide- and silicate-bearing cumulates in some CSEs compared with the upper crust. This storage predisposes the cumulate-hosted compatible CSEs (such as Cu and Au) to be recycled back into the mantle during subduction and delamination, resulting in their low contents in the bulk continental crust and potentially contributing to the scarcity of ore deposits in the upper continental crust. By contrast, differentiation causes the upper oceanic and continental crust to become enriched in incompatible CSEs (such as W) compared with the lower oceanic and continental crust. Consequently, incompatible CSEs are predisposed to become enriched in subduction-zone magmas that contribute to continental crust formation and are less susceptible to removal from the continental crust via delamination compared with the compatible CSEs
Planets in Mean-Motion Resonances and the System Around HD45364
In some planetary systems, the orbital periods of two of its members present
a commensurability, usually known by mean-motion resonance. These resonances
greatly enhance the mutual gravitational influence of the planets. As a
consequence, these systems present uncommon behaviors, and their motions need
to be studied with specific methods. Some features are unique and allow us a
better understanding and characterization of these systems. Moreover,
mean-motion resonances are a result of an early migration of the orbits in an
accretion disk, so it is possible to derive constraints on their formation.
Here we review the dynamics of a pair of resonant planets and explain how their
orbits evolve in time. We apply our results to the HD 45365 planetary system.Comment: invited review, 17 pages, 6 figure
Electron-Spin Excitation Coupling in an Electron Doped Copper Oxide Superconductor
High-temperature (high-Tc) superconductivity in the copper oxides arises from
electron or hole doping of their antiferromagnetic (AF) insulating parent
compounds. The evolution of the AF phase with doping and its spatial
coexistence with superconductivity are governed by the nature of charge and
spin correlations and provide clues to the mechanism of high-Tc
superconductivity. Here we use a combined neutron scattering and scanning
tunneling spectroscopy (STS) to study the Tc evolution of electron-doped
superconducting Pr0.88LaCe0.12CuO4-delta obtained through the oxygen annealing
process. We find that spin excitations detected by neutron scattering have two
distinct modes that evolve with Tc in a remarkably similar fashion to the
electron tunneling modes in STS. These results demonstrate that
antiferromagnetism and superconductivity compete locally and coexist spatially
on nanometer length scales, and the dominant electron-boson coupling at low
energies originates from the electron-spin excitations.Comment: 30 pages, 12 figures, supplementary information include
The validity of using ICD-9 codes and pharmacy records to identify patients with chronic obstructive pulmonary disease
Background: Administrative data is often used to identify patients with chronic obstructive pulmonary disease (COPD), yet the validity of this approach is unclear. We sought to develop a predictive model utilizing administrative data to accurately identify patients with COPD.
Methods: Sequential logistic regression models were constructed using 9573 patients with postbronchodilator spirometry at two Veterans Affairs medical centers (2003-2007). COPD was defined as: 1) FEV1/FVC <0.70, and 2) FEV1/FVC < lower limits of normal. Model inputs included age, outpatient or inpatient COPD-related ICD-9 codes, and the number of metered does inhalers (MDI) prescribed over the one year prior to and one year post spirometry. Model performance was assessed using standard criteria.
Results: 4564 of 9573 patients (47.7%) had an FEV1/FVC < 0.70. The presence of ≥1 outpatient COPD visit had a sensitivity of 76% and specificity of 67%; the AUC was 0.75 (95% CI 0.74-0.76). Adding the use of albuterol MDI increased the AUC of this model to 0.76 (95% CI 0.75-0.77) while the addition of ipratropium bromide MDI increased the AUC to 0.77 (95% CI 0.76-0.78). The best performing model included: ≥6 albuterol MDI, ≥3 ipratropium MDI, ≥1 outpatient ICD-9 code, ≥1 inpatient ICD-9 code, and age, achieving an AUC of 0.79 (95% CI 0.78-0.80).
Conclusion: Commonly used definitions of COPD in observational studies misclassify the majority of patients as having COPD. Using multiple diagnostic codes in combination with pharmacy data improves the ability to accurately identify patients with COPD.Department of Veterans Affairs, Health Services Research and Development (DHA), American Lung Association (CI- 51755-N) awarded to DHA, the American Thoracic Society Fellow Career Development AwardPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/84155/1/Cooke - ICD9 validity in COPD.pd
Ab initio alpha-alpha scattering
Processes involving alpha particles and alpha-like nuclei comprise a major
part of stellar nucleosynthesis and hypothesized mechanisms for thermonuclear
supernovae. In an effort towards understanding alpha processes from first
principles, we describe in this letter the first ab initio calculation of
alpha-alpha scattering. We use lattice effective field theory to describe the
low-energy interactions of nucleons and apply a technique called the adiabatic
projection method to reduce the eight-body system to an effective two-cluster
system. We find good agreement between lattice results and experimental phase
shifts for S-wave and D-wave scattering. The computational scaling with
particle number suggests that alpha processes involving heavier nuclei are also
within reach in the near future.Comment: 6 pages, 6 figure
Bioprospecting Finds the Toughest Biological Material: Extraordinary Silk from a Giant Riverine Orb Spider
Background
Combining high strength and elasticity, spider silks are exceptionally tough, i.e., able to absorb massive kinetic energy before breaking. Spider silk is therefore a model polymer for development of high performance biomimetic fibers. There are over 41.000 described species of spiders, most spinning multiple types of silk. Thus we have available some 200.000+ unique silks that may cover an amazing breadth of material properties. To date, however, silks from only a few tens of species have been characterized, most chosen haphazardly as model organisms (Nephila) or simply from researchers' backyards. Are we limited to ‘blindly fishing’ in efforts to discover extraordinary silks? Or, could scientists use ecology to predict which species are likely to spin silks exhibiting exceptional performance properties?
Methodology
We examined the biomechanical properties of silk produced by the remarkable Malagasy ‘Darwin's bark spider’ (Caerostris darwini), which we predicted would produce exceptional silk based upon its amazing web. The spider constructs its giant orb web (up to 2.8 m2) suspended above streams, rivers, and lakes. It attaches the web to substrates on each riverbank by anchor threads as long as 25 meters. Dragline silk from both Caerostris webs and forcibly pulled silk, exhibits an extraordinary combination of high tensile strength and elasticity previously unknown for spider silk. The toughness of forcibly silked fibers averages 350 MJ/m3, with some samples reaching 520 MJ/m3. Thus, C. darwini silk is more than twice tougher than any previously described silk, and over 10 times better than Kevlar®. Caerostris capture spiral silk is similarly exceptionally tough.
Conclusions
Caerostris darwini produces the toughest known biomaterial. We hypothesize that this extraordinary toughness coevolved with the unusual ecology and web architecture of these spiders, decreasing the likelihood of bridgelines breaking and collapsing the web into the river. This hypothesis predicts that rapid change in material properties of silk co-occurred with ecological shifts within the genus, and can thus be tested by combining material science, behavioral observations, and phylogenetics. Our findings highlight the potential benefits of natural history–informed bioprospecting to discover silks, as well as other materials, with novel and exceptional properties to serve as models in biomimicry.Primary funding for this work came from the Slovenian Research Agency (grant Z1-9799-0618-07 to I. Agnarsson), the National Geographic Society (grant 8655-09 to the authors), and the National Science Foundation (grants DBI-0521261, DEB-0516038 and IOS-0745379 to T. Blackledge). Additional funding came from the European Community 6th Framework Programme (a Marie Curie International Reintegration Grant MIRG-CT-2005 036536 to M. Kuntner). The 2001 field work was supported by the Sallee Charitable Trust grant to I. Agnarsson and M. Kuntner and by a United States National Science Foundation grant (DEB-9712353) to G. Hormiga and J. A. Coddington. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.Peer reviewe
Fast synthesis of platinum nanopetals and nanospheres for highly-sensitive non-enzymatic detection of glucose and selective sensing of ions
Novel methods to obtain Pt nanostructured electrodes have raised particular interest due to their high performance in electrochemistry. Several nanostructuration methods proposed in the literature use costly and bulky equipment or are time-consuming due to the numerous steps they involve. Here, Pt nanostructures were produced for the first time by one-step template-free electrodeposition on Pt bare electrodes. The change in size and shape of the nanostructures is proven to be dependent on the deposition parameters and on the ratio between sulphuric acid and chloride-complexes (i.e., hexachloroplatinate or tetrachloroplatinate). To further improve the electrochemical properties of electrodes, depositions of Pt nanostructures on previously synthesised Pt nanostructures are also performed. The electroactive surface areas exhibit a two order of magnitude improvement when Pt nanostructures with the smallest size are used. All the biosensors based on Pt nanostructures and immobilised glucose oxidase display higher sensitivity as compared to bare Pt electrodes. Pt nanostructures retained an excellent electrocatalytic activity towards the direct oxidation of glucose. Finally, the nanodeposits were proven to be an excellent solid contact for ion measurements, significantly improving the time-stability of the potential. The use of these new nanostructured coatings in electrochemical sensors opens new perspectives for multipanel monitoring of human metabolism
Evidence for phonon skew scattering in the spin Hall effect of platinum
\u3cp\u3eWe measure and analyze the effective spin Hall angle of platinum in the low-residual resistivity regime by second-harmonic measurements of the spin-orbit torques for a multilayer of Pt|Co|AlOx. An angular-dependent study of the torques allows us to extract the effective spin Hall angle responsible for the damping-like torque in the system. We observe a strikingly nonmonotonic and reproducible temperature dependence of the torques. This behavior is compatible with recent theoretical predictions which include both intrinsic and extrinsic (impurities and phonons) contributions to the spin Hall effect at finite temperatures.\u3c/p\u3
Common Genetic Variants Explain the Majority of the Correlation Between Height and Intelligence : The Generation Scotland Study
Creative Commons Attribution LicensePeer reviewedPublisher PD
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