2,453 research outputs found
The fluorine-NHC gauche effect: a structural and computational study
Herein, we report the synthesis and X-ray structural analysis of a collection of fluorinated metal
N-heterocyclic carbenes (Ag, Au, Pd, Rh, Ir) and their precursor salts. The common structural
feature of these species is a flanking fluoroethyl group which is either freely rotating or
embedded within a bicyclic framework. Solid state analysis confirmed a gauche conformational
preference in all cases with the fluorine adopting a syn clinal arrangement (ϕ[NCCF] ~ 60°) with
respect to the triazolium nitrogen at the vicinal position of the NHC. A density functional theory
analysis was employed to quantify these effects and evaluate the influence of electronic
modulation of the carbenic carbon [(C=N+); neutral carbene (C:); metal-bound carbene (C=M)],
on the relative gauche / anti preference, thus highlighting the potential of this conformational
phenomenon as a useful molecular design strategy for controlling the topology of organometallic
complexes
Ending Political Discrimination in the Workplace
Currently, a significant disparity exists in workplace legal protections for an employee’s political affiliation. On one hand, public sector (federal, state, or local government) employees enjoy a bevy of protections. For example, twenty million state and local government employees rely on the First Amendment (and 42 U.S.C. § 1983) to guard against workplace discrimination based on political affiliation. Over two million federal government civil service employees lean on the Civil Service Reform Act of 1978 (CSRA) to provide that same protection
Overstating the evidence - double counting in meta-analysis and related problems
Background: The problem of missing studies in meta-analysis has received much attention. Less attention has been paid to the more serious problem of double counting of evidence.
Methods: Various problems in overstating the precision of results from meta-analyses are described and illustrated with examples, including papers from leading medical journals. These problems include, but are not limited to, simple double-counting of the same studies, double counting of some aspects of the studies, inappropriate imputation of results, and assigning spurious precision to individual studies.
Results: Some suggestions are made as to how the quality and reliability of meta-analysis can be improved. It is proposed that the key to quality in meta-analysis lies in the results being transparent and checkable.
Conclusions: Existing quality check lists for meta-analysis do little to encourage an appropriate attitude to combining evidence and to statistical analysis. Journals and other relevant organisations should encourage authors to make data available and make methods explicit. They should also act promptly to withdraw meta-analyses when mistakes are found
Hybrid Local-Order Mechanism for Inversion Symmetry Breaking
Using classical Monte Carlo simulations, we study a simple statistical
mechanical model of relevance to the emergence of polarisation from local
displacements on the square and cubic lattices. Our model contains two key
ingredients: a Kitaev-like orientation-dependent interaction between nearest
neighbours, and a steric term that acts between next-nearest neighbours. Taken
by themselves, each of these two ingredients is incapable of driving long-range
symmetry breaking, despite the presence of a broad feature in the corresponding
heat capacity functions. Instead each component results in a "hidden"
transition on cooling to a manifold of degenerate states, the two manifolds are
different in the sense that they reflect distinct types of local order.
Remarkably, their intersection---\emph{i.e.} the ground state when both
interaction terms are included in the Hamiltonian---supports a spontaneous
polarisation. In this way, our study demonstrates how local ordering mechanisms
might be combined to break global inversion symmetry in a manner conceptually
similar to that operating in the "hybrid" improper ferroelectrics. We discuss
the relevance of our analysis to the emergence of spontaneous polarisation in
well-studied ferroelectrics such as BaTiO and KNbO.Comment: 8 pages, 8 figure
Top-down Dendritic Input Increases the Gain of Layer 5 Pyramidal Neurons
The cerebral cortex is organized so that an important component of feedback input from higher to lower cortical areas arrives at the distal apical tufts of pyramidal neurons. Yet, distal inputs are predicted to have much less impact on firing than proximal inputs. Here we show that even weak asynchronous dendritic input to the distal tuft region can significantly increase the gain of layer 5 pyramidal neurons and thereby the output of columns in the primary somatosensory cortex of the rat. Noisy currents injected in ramps at different dendritic locations showed that the initial slope of the frequency-current (f/I) relationship increases with the distance of the current injection from the soma. The increase was due to the interaction of dendritic depolarization with back-propagating APs which activated dendritic calcium conductances. Gain increases were accompanied by a change of firing mode from isolated spikes to bursting where the timing of bursts coded the presence of coincident somatic and dendritic inputs. We propose that this dendritic gain modulation and the timing of bursts may serve to associate top-down and bottom-up input on different time scale
Harold Jeffreys's Theory of Probability Revisited
Published exactly seventy years ago, Jeffreys's Theory of Probability (1939)
has had a unique impact on the Bayesian community and is now considered to be
one of the main classics in Bayesian Statistics as well as the initiator of the
objective Bayes school. In particular, its advances on the derivation of
noninformative priors as well as on the scaling of Bayes factors have had a
lasting impact on the field. However, the book reflects the characteristics of
the time, especially in terms of mathematical rigor. In this paper we point out
the fundamental aspects of this reference work, especially the thorough
coverage of testing problems and the construction of both estimation and
testing noninformative priors based on functional divergences. Our major aim
here is to help modern readers in navigating in this difficult text and in
concentrating on passages that are still relevant today.Comment: This paper commented in: [arXiv:1001.2967], [arXiv:1001.2968],
[arXiv:1001.2970], [arXiv:1001.2975], [arXiv:1001.2985], [arXiv:1001.3073].
Rejoinder in [arXiv:0909.1008]. Published in at
http://dx.doi.org/10.1214/09-STS284 the Statistical Science
(http://www.imstat.org/sts/) by the Institute of Mathematical Statistics
(http://www.imstat.org
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