792 research outputs found
Circus-specific extension of the International Olympic Committee consensus statement: Methods for recording and reporting of epidemiological data on injury and illness in sport 2020
Indepth knowledge of injury and illness epidemiology in circus arts is lacking. Comparing results across studies is difficult due to inconsistent methods and definitions. In 2020, the International Olympic Committee (IOC) consensus group proposed a standard method for recording and reporting epidemiological data on injuries and illnesses in sports and stated that sport-specific extension statements are needed to capture the context of each sport. This is the circus-specific extension to be used with the IOC consensus statement. International circus arts researchers in injury and illness epidemiology and performing arts medicine formed a consensus working group. Consensus statement development included a review of literature, creation of an initial draft by the working group, feedback from external reviewers, integration of feedback into the second draft and a consensus on the final document. This consensus statement contains circus-specific information on (1) injury definitions and characteristics; (2) measures of severity and exposure, with recommendations for calculating the incidence and prevalence; (3) a healthcare practitioner report form; (4) a self-report form capturing health complaints with training and performance exposure; and (5) a demographic, health history and circus experience intake questionnaire. This guideline facilitates comparing results across studies and enables combining data sets on injuries in circus arts. This guideline informs circus-specific injury prevention, rehabilitation, and risk management to improve the performance and health of circus artists
Statistical analysis of ENDOR spectra
Electronânuclear double resonance (ENDOR) measures the hyperfine interaction of magnetic nuclei with paramagnetic centers and is hence a powerful tool for spectroscopic investigations extending from biophysics to material science. Progress in microwave technology and the recent availability of commercial electron paramagnetic resonance (EPR) spectrometers up to an electron Larmor frequency of 263 GHz now open the opportunity for a more quantitative spectral analysis. Using representative spectra of a prototype amino acid radical in a biologically relevant enzyme, the Yâ122 in Escherichia coli ribonucleotide reductase, we developed a statistical model for ENDOR data and conducted statistical inference on the spectra including uncertainty estimation and hypothesis testing. Our approach in conjunction with 1H/2H isotopic labeling of Yâ122 in the protein unambiguously established new unexpected spectral contributions. Density functional theory (DFT) calculations and ENDOR spectral simulations indicated that these features result from the beta-methylene hyperfine coupling and are caused by a distribution of molecular conformations, likely important for the biological function of this essential radical. The results demonstrate that model-based statistical analysis in combination with state-of-the-art spectroscopy accesses information hitherto beyond standard approaches
CAACâBased Thiele and Schlenk Hydrocarbons
Diradicals have been of tremendous interest for over a century ever since the first reports of p â and m âphenyleneâbridged diphenylmethylradicals in 1904 by Thiele and 1915 by Schlenk. Reported here are the first examples of cyclic(alkyl)(amino)carbene (CAAC) analogues of Thiele's hydrocarbon, a KekulĂ© diradical, and Schlenk's hydrocarbon, a nonâKekulĂ© diradical, without using CAAC as a precursor. The CAAC analogue of Thiele's hydrocarbon has a singlet ground state, whereas the CAAC analogue of Schlenk's hydrocarbon contains two unpaired electrons. The latter forms a dimer, by an intermolecular double headâtoâtail dimerization. This straightforward synthetic methodology is modular and can be extended for the generation of redoxâactive organic compounds
NonâIdentical Stepwise Reversible DoubleâRedox Coupled Bond Activation Reactions
This work presents a stepwise reversible twoâelectron transfer induced hydrogen shift leading to the conversion of a bisâpyrrolinium cation to an E âdiaminoalkene and vice versa. Remarkably, the forward and the reverse reaction, which are both reversible, follow two completely different reaction pathways. Establishing such unprecedented property in this type of processes was possible by developing a novel synthetic route towards the starting dication. All intermediates involved in both the forward and the backward reactions were comprehensively characterized by a combination of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and theoretical methods. The presented synthetic route opens up new possibilities for the generation of multiâpyrrolinium cation scaffoldâbased organic redox systems, which constitute decidedly soughtâafter molecules in contemporary chemistry
Allosteric Inhibition of Human Ribonucleotide Reductase by dATP Entails the Stabilization of a Hexamer
Ribonucleotide reductases (RNRs) are responsible for all de novo biosynthesis of DNA precursors in nature by catalyzing the conversion of ribonucleotides to deoxyribonucleotides. Because of its essential role in cell division, human RNR is a target for a number of anticancer drugs in clinical use. Like other class Ia RNRs, human RNR requires both a radical-generation subunit (ÎČ) and nucleotide-binding subunit (α) for activity. Because of their complex dependence on allosteric effectors, however, the active and inactive quaternary forms of many class Ia RNRs have remained in question. Here, we present an X-ray crystal structure of the human α subunit in the presence of inhibiting levels of dATP, depicting a ring-shaped hexamer (α[subscript 6]) where the active sites line the inner hole. Surprisingly, our small-angle X-ray scattering (SAXS) results indicate that human α forms a similar hexamer in the presence of ATP, an activating effector. In both cases, α[subscript 6] is assembled from dimers (α[subscript 2]) without a previously proposed tetramer intermediate (α[subscript 4]). However, we show with SAXS and electron microscopy that at millimolar ATP, the ATP-induced α[subscript 6] can further interconvert with higher-order filaments. Differences in the dATP- and ATP-induced α[subscript 6] were further examined by SAXS in the presence of the ÎČ subunit and by activity assays as a function of ATP or dATP. Together, these results suggest that dATP-induced α[subscript 6] is more stable than the ATP-induced α6 and that stabilization of this ring-shaped configuration provides a mechanism to prevent access of the ÎČ subunit to the active site of α.National Institutes of Health (U.S.) (GM100008)National Institutes of Health (U.S.) (Grant GM29595)Massachusetts Institute of Technology. Undergraduate Research Opportunities Progra
The Familial Clustering of Age at Menarche in Extended Twin Families
The timing of puberty is complex, possibly involving many genetic factors that may interact with environmental influences. Familial resemblance for age at menarche was studied in a sample of 4,995 female twins, 1,296 sisters, 2,946 mothers and 635 female spouses of male twins. They had indicated their age at menarche as part of a larger longitudinal survey. We assessed assortative mating for age at menarche, geneâenvironment interaction effects and estimated the heritability of individual differences in pubertal timing. There was significant evidence of geneâenvironment interaction, accounting for 1.5% of the variance. There was no indication of consistent mate assortment on age at menarche. Individual differences in age at menarche are highly heritable, with additive genetic factors explaining at least 70% of the true variation. An additional 1.5% of the variation can be explained by a genotypeâenvironment interaction effect where environmental factors are more important in individuals genetically predisposed for late menarche
Phase transition in the collisionless regime for wave-particle interaction
Gibbs statistical mechanics is derived for the Hamiltonian system coupling
self-consistently a wave to N particles. This identifies Landau damping with a
regime where a second order phase transition occurs. For nonequilibrium initial
data with warm particles, a critical initial wave intensity is found: above it,
thermodynamics predicts a finite wave amplitude in the limit of infinite N;
below it, the equilibrium amplitude vanishes. Simulations support these
predictions providing new insight on the long-time nonlinear fate of the wave
due to Landau damping in plasmas.Comment: 12 pages (RevTeX), 2 figures (PostScript
Partial Description of Quantum States
One of the most central and controversial element of quantum mechanics is the
use of non zero vectors of a Hilbert space (or, more generally, of one
dimension subspaces) for representing the state of a quantum system. In
particular, the question whether such a representation is complete has been
debated since almost the early days of quantum mechanics. In this article, we
develop an alternate way to formalize knowledge about the state of quantum
systems, based solely on experimentally accessible elements, namely on outcomes
of finite measurements. We introduce what we call partial description which,
given a feasible measurement, indicates some outcomes which are known to be
impossible (i.e. known to have a probability equal to 0 to occur) and hence
have to be discarded. Then, we introduce partial states (which are partial
descriptions providing as much information as possible) and compare this way to
describe quantum states to the orthodox one, using vector rays. Finally, we
show that partial states allow to describe quantum states in a strictly more
expressive way that the orthodox description does
Engineering tyrosine-based electron flow pathways in proteins: The case of aplysia myoglobin
Tyrosine residues can act as redox cofactors that provide an electron transfer ("hole-hopping") route that enhances the rate of ferryl heme iron reduction by externally added reductants, for example, ascorbate. Aplysia fasciata myoglobin, having no naturally occurring tyrosines but 15 phenylalanines that can be selectively mutated to tyrosine residues, provides an ideal protein with which to study such through-protein electron transfer pathways and ways to manipulate them. Two surface exposed phenylalanines that are close to the heme have been mutated to tyrosines (F42Y, F98Y). In both of these, the rate of ferryl heme reduction increased by up to 3 orders of magnitude. This result cannot be explained in terms of distance or redox potential change between donor and acceptor but indicates that tyrosines, by virtue of their ability to form radicals, act as redox cofactors in a new pathway. The mechanism is discussed in terms of the Marcus theory and the specific protonation/deprotonation states of the oxoferryl iron and tyrosine. Tyrosine radicals have been observed and quantified by EPR spectroscopy in both mutants, consistent with the proposed mechanism. The location of each radical is unambiguous and allows us to validate theoretical methods that assign radical location on the basis of EPR hyperfine structure. Mutation to tyrosine decreases the lipid peroxidase activity of this myoglobin in the presence of low concentrations of reductant, and the possibility of decreasing the intrinsic toxicity of hemoglobin by introduction of these pathways is discussed. © 2012 American Chemical Society
Bohrification of operator algebras and quantum logic
Following Birkhoff and von Neumann, quantum logic has traditionally been
based on the lattice of closed linear subspaces of some Hilbert space, or, more
generally, on the lattice of projections in a von Neumann algebra A.
Unfortunately, the logical interpretation of these lattices is impaired by
their nondistributivity and by various other problems. We show that a possible
resolution of these difficulties, suggested by the ideas of Bohr, emerges if
instead of single projections one considers elementary propositions to be
families of projections indexed by a partially ordered set C(A) of appropriate
commutative subalgebras of A. In fact, to achieve both maximal generality and
ease of use within topos theory, we assume that A is a so-called Rickart
C*-algebra and that C(A) consists of all unital commutative Rickart
C*-subalgebras of A. Such families of projections form a Heyting algebra in a
natural way, so that the associated propositional logic is intuitionistic:
distributivity is recovered at the expense of the law of the excluded middle.
Subsequently, generalizing an earlier computation for n-by-n matrices, we
prove that the Heyting algebra thus associated to A arises as a basis for the
internal Gelfand spectrum (in the sense of Banaschewski-Mulvey) of the
"Bohrification" of A, which is a commutative Rickart C*-algebra in the topos of
functors from C(A) to the category of sets. We explain the relationship of this
construction to partial Boolean algebras and Bruns-Lakser completions. Finally,
we establish a connection between probability measure on the lattice of
projections on a Hilbert space H and probability valuations on the internal
Gelfand spectrum of A for A = B(H).Comment: 31 page
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