Sequential reactions from catalytic hydroformylation toward the synthesis of amino compounds

Different families of new amino compounds were efficiently synthesized, through optimized sequential processes, involving rhodium catalyzed hydroformylation as the key step. The selection of appropriate hydroformylation catalytic systems and reaction conditions allowed obtaining aldehydes derived from several n-alkyl olefins, cholest-4-ene and 3-vinyl-1H-indole, which were subsequently transformed, in one-pot, in to α-amino acids via hydroformylation/Strecker reaction, and in to tertiary amines via hydroaminomethylation, with excellent yields.     

How different are two chemical structures?

We extend the scope of a recent method for superimposing two molecules ( J. Chem. Phys. 2009, 131, 124126-1-124126-10 ) to include the identification of chiral structures. This methodology is tested by applying it to several organic molecules and water clusters that were subjected to geometry optimization. The accuracy of four simpler, non-superimposing approaches is then analyzed by comparing pairs of structures for argon and water clusters. The structures considered in this work were obtained by a Markovian walk in the coordinate space. First, a random geometry is generated, and then, the iterative application of a mutation operator ensures the creation of increasingly dissimilar structures. The discriminating power of the non-superimposing approaches is tested by comparing the corresponding dissimilarity measures with the root-mean-square distance obtained from the superimposing method. Finally, we showcase the application of those methods to characterize the diversity of solutions in global geometry optimization by evolutionary algorithms.     

Multiplicity of periodic orbits for dynamically convex contact forms

We give a sharp lower bound for the number of geometrically distinct contractible periodic orbits of dynamically convex Reeb flows on prequantizations of symplectic manifolds that are not aspherical. Several consequences of this result are obtained, like a new proof that every bumpy Finsler metric on \(S^n\) carries at least two prime closed geodesics, multiplicity of elliptic and non-hyperbolic periodic orbits for dynamically convex contact forms with finitely many geometrically distinct contractible closed orbits and precise estimates of the number of even periodic orbits of perfect contact forms. We also slightly relax the hypothesis of dynamical convexity. A fundamental ingredient in our proofs is the common index jump theorem due to Y. Long and C. Zhu.     

Hydrophobic/hydrophilic solvation: inferences from Monte Carlo simulations and experiments

In this study Monte Carlo simulations are used to determine the solvation properties of model hydrophobic (xenon and hard sphere) and hydrophilic (dimethyl ether) solutes in SPC/E water. Various contributions to the experimental solvation entropy, including the solvent reorganization entropy, have been determined. The main conclusion drawn, which is in accord with solubility data, is that poor solubility correlates with poor solute-water interaction. At room temperature, energy dominates the aqueous solubility of both hydrophobic and hydrophilic solutes, rather than entropy. However, at higher temperatures the solubility can pass through a minimum, and then entropy becomes dominant. Another interesting finding is the presence of larger than expected cavities in water. Two different simulation results support this finding. This unexpected hollow structure in water explains why a hard sphere solute is more soluble in water than in a comparable hard sphere or Lennard-Jones solvent. Hydrogen bonding causes water to aggregate into clusters that produce a few large cavities rather than many smaller cavities. The propensity for clustering also explains why water gives the illusion of being a low density liquid. Sufficient theoretical apparatus is developed to connect theoretical solvation properties to those measured by simulation and experiment. Finally, based on gas solubility, an intuitive hydrophobic/hydrophilic scale is developed.     

Use of radial basis function networks and near-infrared spectroscopy for the determination of total nitrogen content in soils from Sao Paulo State

Total nitrogen has been determined by using a model developed between the conventional chemical measurements and diffuse reflectance spectra in the near-infrared region. Samples (244) from different types of soils with total nitrogen contents ranging from 0.20 to 13.60% (m/m) were modeled by partial least-squares regression (PLS), multi-layer perceptron feed-forward networks (MLP) and radial basis function networks (RBFN). The RBFN model produced a better square error of prediction (SEP) of 0.048 and R(2) = 0.93 in a procedure that is simpler, faster and less dependent on the initial conditions.     

On the covariantization of the chiral constraints

We show that a complete covariantization of the chiral constraint in the Floreanini-Jackiw necessitates an infinite number of auxiliary Wess-Zumino fields other-wise the covariantization is only partial and unable to remove the nonlocality in the chiral boson operator. We comment on recent works that claim to obtain covariantization through the use of Batalin-Fradkin-Tyutin method, that uses just one Wess-Zumino field.     

A study of π andK production in proton-uranium and oxygen-uranium interactions at 22 GeV/A using decay muons

The like-sign dimuons copiously recorded in the NA 38 experiment both inp-U and O?U reactions at 200 GeV/nucleon are interpreted as resulting from decays of π andK mesons in comparable proportions. The ++/?? ratio is large (?1.7) and ascribed to theK ⁺ being more copiously produced than theK ^?. Both the average transverse momentum and the ++/?? ratio are comparable forp-U and O?U reactions, and both increase only slightly with the transverse energyE _T .