The enantioselective copolymerisation of allylbenzene, 1-allyl-4-(trifluoromethyl)benzene,and 1-allyl-4-methoxybenzene with carbon monoxide

The olefins mentioned in the title were copolymerized with CO in the presence of palladium catalysts modified with dicyclohexyl{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}phosphine. Productivities up to 95 g/(gPd · h) were achieved. The obtained copolymers were recovered in the pure, regio- und stereoregular polyketone structures 3 . The isotactic poly[2-benzyl-1-oxopropane-1,3-diyl] ( 3a ) and its analogues 3b , c were found to isomerize to the corresponding spirocyclic poly[3-(arylmethyl)tetrahydrofuran-2,2-5,5-tetrayl-2-oxy-2-methylene]s 4 in a suspension in CHC13, thus indicating that the spiroketal structure is thermodynamically the most stable for these copolymers. However, the atactic material did not undergo any structural transformation. These results show that regularity at the centers of chirality in the main chain is a prerequisite for the conversion of the polyketone to the spiroketal structure.     

Synthesis of new molecular scaffolds: 3-aza-7,9-dioxa-bicyclo[4.2.1]nonane (8-exo BTKa) and 3-aza-8,10-dioxa-bicyclo[5.2.1]decane (9-exo BTKa) carboxylic acids

Two classes of enantiopure molecular scaffolds were prepared, whose lactam structure formally derives from the coupling between tartaric acid and β- or γ-ketoamines. We labelled these compounds as 8-exo and 9-exo BTKa, indicating the lactam size (8- and 9-membered ring, respectively). Starting from β- and γ-nitroketones, the synthesis involves the ketal formation by (R,R)-dimethyl tartrate. The subsequent amide bond formation occurs during the hydrogenation of the nitro group over Raney-Ni and no expected open chain amine was observed.     

Phase segregation dynamics in particle systems with long range interactions. I. Macroscopic limits

We present and discuss the derivation of a nonlinear nonlocal integrodifferential equation for the macroscopic time evolution of the conserved order parameter (r, t) of a binary alloy undergoing phase segregation. Our model is ad-dimensional lattice gas evolving via Kawasaki exchange with respect to the Gibbs measure for a Hamiltonian which includes both short-range (local) and long-range (nonlocal) interactions. The nonlocal part is given by a pair potential ^dJ(|x–y|), >0 x and y in ^d, in the limit 0. The macroscopic evolution is observed on the spatial scale ^–1 and time scale ^–2, i.e., the density (r, t) is the empirical average of the occupation numbers over a small macroscopic volume element centered atr=x. A rigorous derivation is presented in the case in which there is no local interaction. In a subsequent paper (Part II) we discuss the phase segregation phenomena in the model. In particular we argue that the phase boundary evolutions, arising as sharp interface limits of the family of equations derived in this paper, are the same as the ones obtained from the corresponding limits for the Cahn-Hilliard equation.     

Metastability for the Exclusion Process with Mean-Field Interaction

We consider an exclusion particle system with long-range, mean-field-type interactions at temperature 1/β. The hydrodynamic limit of such a system is given by an integrodifferential equation with one conservation law on the circle $C$ : it is the gradient flux of the Kac free energy functional F _β. For β≤1, any constant function with value m ∈ [?1, +1] is the global minimizer of F _β in the space $\{ u:\int_C {u(x)} \,dx = m\} $ . For β>1, F _β restricted to $\{ u:\int_C {u(x)} \,dx = m\} $ may have several local minima: in particular, the constant solution may not be the absolute minimizer of F _β. We therefore study the long-time behavior of the particle system when the initial condition is close to a homogeneous stable state, giving results on the time of exit from (suitable) subsets of its domain of attraction. We follow the Freidlin–Wentzell approach: first, we study in detail F _β together with the time asymptotics of the solution of the hydrodynamic equation; then we study the probability of rare events for the particle system, i.e., large deviations from the hydrodynamic limit.     

Blockade of stress-induced increase of glutamate release in the rat prefrontal/frontal cortex by agomelatine involves synergy between melatonergic and 5-HT2C receptor-dependent pathways

Background

Agomelatine is a melatonergic receptor agonist and a 5HT_2C receptor antagonist that has shown antidepressant efficacy. In order to analyze separately the effect of the two receptorial components, rats were chronically treated with agomelatine, melatonin (endogenous melatonergic agonist), or S32006 (5-HT_2C antagonist), and then subjected to acute footshock-stress.

Results

Only chronic agomelatine, but not melatonin or S32006, completely prevented the stress-induced increase of glutamate release in the rat prefrontal/frontal cortex.

Conclusions

These results suggest a potential synergy between melatonergic and serotonergic pathways in the action of agomelatine.     

Dynamical Aspects of Mean Field Plane Rotators and the Kuramoto Model

The Kuramoto model has been introduced in order to describe synchronization phenomena observed in groups of cells, individuals, circuits, etc. We look at the Kuramoto model with white noise forces: in mathematical terms it is a set of N oscillators, each driven by an independent Brownian motion with a constant drift, that is each oscillator has its own frequency, which, in general, changes from one oscillator to another (these frequencies are usually taken to be random and they may be viewed as a quenched disorder). The interactions between oscillators are of long range type (mean field). We review some results on the Kuramoto model from a statistical mechanics standpoint: we give in particular necessary and sufficient conditions for reversibility and we point out a formal analogy, in the N→∞ limit, with local mean field models with conservative dynamics (an analogy that is exploited to identify in particular a Lyapunov functional in the reversible set-up). We then focus on the reversible Kuramoto model with sinusoidal interactions in the N→∞ limit and analyze the stability of the non-trivial stationary profiles arising when the interaction parameter K is larger than its critical value K _c . We provide an analysis of the linear operator describing the time evolution in a neighborhood of the synchronized profile: we exhibit a Hilbert space in which this operator has a self-adjoint extension and we establish, as our main result, a spectral gap inequality for every K>K _c .     

On Entropic Reduction of Fluctuations

We point out that there is no general relation between ground state degeneracy and finite-temperature fluctuations for tilted interfaces.     

Baker's yeast reduction of prochiral γ-nitroketones. II. straightforward enantioselective synthesis of 2,7-dimethyl-1,6-dioxaspiro[4.4]nonanes

The baker's yeast reduction of 5-nitro-2,8-nonanedione 2 afforded the corresponding (2S,8S)-5-nitro-2,8-nonanediol3 with complete diastereoselectivity and high enantioselectivity. The conversion of 3 into the thermodynamic (E,E)/(Z,Z) (3:1) mixture of optically active (95% e.e.) 2,7-dimethyl-1,6-dioxaspiro[4.4]nonanes 5 was then achieved by spontaneous cyclization under the acidic conditions of the Nef reaction.