Enantioselective synthesis of C2-functionalized, N-protected morpholines and orthogonally N,N'-protected piperazines via organocatalysis

In this Letter, we describe a novel three-step, one-pot procedure for the enantioselective synthesis of N-benzyl protected morpholines and orthogonally N,N'-protected piperazines with chiral alkyl groups installed at the C2 position of each heterocyclic core via organocatalysis. This methodology allows for the rapid preparation of functionalized morpholines and piperazines that are not readily accessible through any other chemistry in good to excellent % ee (55-98% ee).     

Proliferative reactive gliosis is compatible with glial metabolic support and neuronal function

Background

Trail-making tests, such as the Concept Shifting Task (CST), can be used to test the effects of treatment on cognitive performance over time in various neuropsychological disorders. However, cognitive performance in such experimental designs might improve as a result of the practice obtained during repeated testing rather than the treatment itself. The current study investigated if practice affects the accuracy and duration of performance on the repeatedly administered Concept Shifting Task modified to make it resistant to practice (mCST). The mCST was administered to 54 healthy participants twice a day, before and after a short break, for eight days. Results. The ANOVA and meta-analysis showed that there was no improvement in the mCST accuracy on the last vs. the first trial (Hedges' g = .14, p = .221) or within the session (after vs. before the break on all days; g = .01, p = .922). However, the participants performed the task faster on the last vs. the first trial (g = -.75, p < .001) and after vs. before the break on all days (g = -.12, p = .002). Conclusions. Repeated administration of the mCST does not affect the accuracy of performance on the test. However, practice might contribute to faster performance on the mCST over time and within each session.     

Neutron and proton transverse emission ratio measurements and the density dependence of the asymmetry term of the nuclear equation of state

Recent measurements of preequilibrium neutron and proton transverse emission from (112,124)Sn+(112,124)Sn reactions at 50 MeV/A have been completed at the National Superconducting Cyclotron Laboratory. Free nucleon transverse emission ratios are compared to those of A=3 mirror nuclei. Comparisons are made to Boltzmann-Uehling-Uhlenbeck (BUU) transport calculations and conclusions concerning the density dependence of the asymmetry term of the nuclear equation of state at subnuclear densities are made. Comparison to BUU model predictions indicate a density dependence of the asymmetry energy that is closer to a form in which the asymmetry energy increases as the square root of the density for the density region studied. A coalescent-invariant analysis is introduced as a means of reducing suggested difficulties with cluster emission in total nucleon emission.     

Negative thermal expansion in ZrW2O8: mechanisms, rigid unit modes, and neutron total scattering

The local structure of the low-temperature ordered phase of the negative thermal expansion (NTE) material has been investigated by reverse Monte Carlo (RMC) modeling of neutron total scattering data. We obtain, for the first time, quantitative measurements of the extent to which the and polyhedra move as rigid units, and we show that these values are consistent with the predictions of rigid unit mode theory. We suggest that rigid unit modes are associated with the NTE. Our results do not support a recent interpretation of x-ray-absorption fine structure spectroscopy data in terms of a larger rigid structural component involving the Zr-O-W linkage.     

Nonequilibrium raftlike membrane domains under continuous recycling

We present a model for the kinetics of spontaneous membrane domain (raft) assembly that includes the effect of membrane recycling ubiquitous in living cells. We show that domains can have a broad power-law distribution with an average radius that scales with the 1/4 power of the domain lifetime when the line tension at the domain edges is large. For biologically reasonable recycling and diffusion rates, the average domain radius is in the tens of nm range, consistent with observations. This represents one possible link between signaling (involving rafts) and traffic (recycling) in cells. Finally, we present evidence that suggests that the average raft size may be the same for all scale-free recycling schemes.     

Central Limit Theorems for the Shrinking Target Problem

Suppose B _i :=B(p,r _i ) are nested balls of radius r _i about a point p in a dynamical system (T,X,μ). The question of whether T ⁱ x∈B _i infinitely often (i.o.) for μ a.e. x is often called the shrinking target problem. In many dynamical settings it has been shown that if $E_{n}:=\sum_{i=1}^{n} \mu(B_{i})$ diverges then there is a quantitative rate of entry and $\lim_{n\to\infty} \frac{1}{E_{n}} \sum_{j=1}^{n} 1_{B_{i}} (T^{i} x) \to1$ for μ a.e. x∈X. This is a self-norming type of strong law of large numbers. We establish self-norming central limit theorems (CLT) of the form $\lim_{ n\to\infty} \frac{1}{a_{n}} \sum_{i=1}^{n} [1_{B_{i}} (T^{i} x)-\mu(B_{i})] \to N(0,1)$ (in distribution) for a variety of hyperbolic and non-uniformly hyperbolic dynamical systems, the normalization constants are $a^{2}_{n} \sim E [\sum_{i=1}^{n} 1_{B_{i}} (T^{i} x)-\mu(B_{i})]^{2}$ . Dynamical systems to which our results apply include smooth expanding maps of the interval, Rychlik type maps, Gibbs-Markov maps, rational maps and, in higher dimensions, piecewise expanding maps. For such central limit theorems the main difficulty is to prove that the non-stationary variance has a limit in probability.