UNUSUAL CRYSTALLIZATION AND MELTING PROCESSES OF AN OPTICALLY ACTIVE POLYOLEFIN： ISOTACTIC POLY（（S）-4-METHYL-HEXENE-1）

Polyolefins that bear a chiral side chain (typically an isobutyl group) experience a so-called macromolecular amplification of chirality: the chiral side-chain induces a slight preference for either tg or tg- main chain conformation. This slight conformational bias is amplified cooperatively along the chain, and results in preferred chirality of the main chain helical conformations. As a result, these polymers display a liquid-crystal (LC) phase both in solution and, in the melt as a transient phase on the way to crystallization. The existence of two processes (melt-LC and LC-crystal transitions) results in unconventional behaviors that were first analyzed by Pino and collaborators back in 1975. These polymers also offer a means to test the structural consequences of recently introduced crystallization schemes. These schemes postulate the formation of a transient liquid-crystal phase as a general scheme for polymer crystallization.     

Existence and uniqueness for p-Laplace equations involving singular nonlinearities

We consider quasilinear elliptic equations involving the p-Laplacian and singular nonlinearities. We prove comparison principles and we deduce some uniqueness results.     

N-metalated imines by reaction of 1,1-diethoxybut-2-ene with aromatic nitriles, as useful intermediates for the synthesis of substituted pyrimidines and cyclopentenones

A new approach to the synthesis of pyrimidines and cyclopentenones is described. The method exploits the reactivity of alpha,beta-unsaturated acetals with aromatic nitriles in the presence of the Schlosser's superbase LIC-KOR.     

Stochastic weighted variational inequalities in non-pivot Hilbert spaces with applications to a transportation model

A class of stochastic weighted variational inequalities in non-pivot Hilbert spaces is proposed. Existence and continuity results are proved. These theoretical results play a prominent role in order to introduce a new weighted transportation model with uncertainty. Moreover, they allow to establish the equivalence between the random weighted equilibrium principle and a suitable stochastic weighted variational inequality. At the end, a numerical model is discussed.     

Assessing the cost of capital for longevity risk

The cost of capital is a key element of the embedded value methodology for the valuation of a life business. Further, under some solvency approaches (in particular, the Swiss Solvency Test and the developing Solvency 2 project) assessing the cost of capital constitutes a step in determining the required capital allocation.Whilst the cost of capital is usually meant as a reward for the risks encumbering a given life portfolio, in actuarial practice the relevant parameter has been traditionally chosen, at least to some extent, inconsistently with such risks. The adoption of market-consistent valuations has then been advocated to reach a common standard.A market-consistent value usually acknowledges a reward to shareholders’ capital as long as the market does, namely if the risk is systematic or undiversifiable. When dealing with a life annuity portfolio (or a pension plan), an important example of systematic risk is provided by the longevity risk, i.e. the risk of systematic deviations from the forecasted mortality trend. Hence, a market-consistent approach should provide appropriate valuation tools.In this paper we refer to a portfolio of immediate life annuities and we focus on longevity risk. Our purpose is to design a framework for a valuation of the portfolio which is market-consistent, and therefore based on a risk-neutral argument, while involving some of the basic items of a traditional valuation, viz best estimate future flows and allocated capital. This way, we try to reconcile the traditional with a market-consistent (or risk-neutral) approach. This allows us, in particular, to translate the results obtained under the risk-neutral approach in terms of a properly redefined embedded value.     

Click chemistry on a ruthenium polypyridine complex. An efficient and versatile synthetic route for the synthesis of photoactive modular assemblies

In this Communication, we present the synthesis and use of [Ru(bpy)(2)(bpy-CCH)](2+), a versatile synthon for the construction of more sophisticated dyads by means of click chemistry. The resulting chromophore-acceptor or -donor complexes have been studied by flash photolysis and are shown to undergo efficient electron transfer to/from the chromophore. Additionally, the photophysical and chemical properties of the original chromophore remain intact, making it a very useful component for the preparation of visible-light-active dyads.     

New enantioselective entry to cycloheptane amino acid polyols

[reaction: see text] A diversity-oriented protocol has been developed for the assembly of densely hydroxylated cycloheptane amino acids via succession of a vinylogous Mukaiyama aldol reaction (VMAR), a Morita-Baylis-Hillman reaction (MBHR), and an intramolecular pinacol coupling reaction (IPCR). The plan utilizes D- or L-configured glyceraldehyde derivatives as "chiral" surrogates of glyoxal and N-[(tert-butoxycarbonyl)-2-(tert-butyldimethylsilyl)oxy]pyrrole as the synthetic equivalent of the alpha,gamma-dianion of gamma-aminobutanoic acid. The parallel, asymmetric syntheses of four cycloheptane representatives proceed with high diastereocontrol and virtually complete enantioselectivity in ten steps and overall yields of 15-37%.