Generation and intramolecular reactivity of acyl radicals from alkynylthiol esters under reducing tin-free conditions

[reaction: see text] The radical chain reaction of benzenethiol with alkynylthiol esters provides a new, valuable protocol for the tin-free generation of acyl radicals that arise from intramolecular substitution at sulfur by the initial sulfanylvinyl radicals.     

On Nonlinear Integro-differential Operators in Generalized Orlicz–Sobolev Spaces

A nonlinear integral operator T of the form (Tf)(s)=∫_G K(t, f (σ(s, t))) dμ(t), for sG, is defined and investigated in the measure space (G, Σ, μ), where f and K are vector-valued functions with values in normed linear spaces E and F, respectively. The results are applied to the case of integro-differential operators in generalized Orlicz–Sobolev spaces. There are studied problems of existence, embeddings, and approximation by means of T.     

Constraining extended theories of gravity using Solar System tests

Solar System tests give nowadays constraints on the estimated value of the cosmological constant, which can be accurately derived from different experiments regarding gravitational redshift, light deflection, gravitational time-delay and geodesic precession. Assuming that each reasonable theory of gravitation should satisfy Solar System tests, we use these limits on the estimated value of the cosmological constant to constrain extended theories of Gravity, which are nowadays studied as possible theories for cosmological models and provide viable solutions to the cosmological constant problem and the explanation of the present acceleration of the Universe. We obtain that the estimated values, from Solar System tests, for the parameters appearing in the extended theories of Gravity are orders of magnitude bigger than the values obtained in the framework of cosmologically relevant theories.     

Fluorous phase transfer catalysts: From onium salts to crown ethers

Fluorous quaternary ammonium and phosphonium salts, as well as fluorous macrocyclic ligands, such as crown and aza-crown ethers, have been gradually emerging as viable alternatives to classical phase transfer catalysts. The major results thus far obtained in this burgeoning field will be the focus of this review.     

Second-Order Covariant Tensor Decomposition in Curved Spacetime

Local four-dimensional tensor decomposition formulae for generic vectors and 2-tensors in spacetime, in terms of scalar and antisymmetric covariant tensor potentials, are studied within the framework of tensor distributions. Earlier first-order decompositions are extended to include the case of four-dimensional symmetric 2-tensors and new second-order decompositions are introduced.     

Asymptotic Information-Theoretic Detection of Dynamical Organization in Complex Systems

The identification of emergent structures in complex dynamical systems is a formidable challenge. We propose a computationally efficient methodology to address such a challenge, based on modeling the state of the system as a set of random variables. Specifically, we present a sieving algorithm to navigate the huge space of all subsets of variables and compare them in terms of a simple index that can be computed without resorting to simulations. We obtain such a simple index by studying the asymptotic distribution of an information-theoretic measure of coordination among variables, when there is no coordination at all, which allows us to fairly compare subsets of variables having different cardinalities. We show that increasing the number of observations allows the identification of larger and larger subsets. As an example of relevant application, we make use of a paradigmatic case regarding the identification of groups in autocatalytic sets of reactions, a chemical situation related to the origin of life problem.     

Infrared Problem for the Nelson Model on Static Space-Times

We consider the Nelson model on some static space-times and investigate the problem of existence of a ground state. Nelson models with variable coefficients arise when one replaces in the usual Nelson model the flat Minkowski metric by a static metric, allowing also the boson mass to depend on position. We investigate the existence of a ground state of the Hamiltonian in the presence of the infrared problem, i.e. assuming that the boson mass m(x) tends to 0 at spatial infinity. We show that if m(x) ≥ C |x|⁻¹ at infinity for some C > 0 then the Nelson Hamiltonian has a ground state.     

Observational constraints on loop quantum cosmology

In the inflationary scenario of loop quantum cosmology in the presence of inverse-volume corrections, we give analytic formulas for the power spectra of scalar and tensor perturbations convenient to compare with observations. Since inverse-volume corrections can provide strong contributions to the running spectral indices, inclusion of terms higher than the second-order runnings in the power spectra is crucially important. Using the recent data of cosmic microwave background and other cosmological experiments, we place bounds on the quantum corrections.