Synthesis of EDTA core dendrimers through a consecutive esterification-CuAAC process

A novel class of thermostable G0 and G1-dendrimers was synthesized from the coupling of both propargyl and azido esters derived from EDTA through copper catalyzed azide-alkyne cycloaddition. The branching and size in these compounds were controlled by a simple azide-alkyne group position change in the CuAAC reaction in conjunction with the use of 1,3-diazido-propan-2-ol as a polyfunctional compound.     

Binding of Ionic Pyrene Derivatives to Polyelectrolytes. A Uv Absorption and Fluorescence Study

Abstract

The binding of pyrenesulfonic acid and pyrenebutyric acid to poly(vinyl benzyl trimethylammonium) chloride was investigated by UV and fluorescence spectroscopy. It was found that the binding constant was 7.5 × 10⁴ and 3.5 × 10⁴M^?1, respectively. The addition of the polyelectrolyte quenches the fluorescence of the pyrene group, and at the same time the typical excimer emission appears. This emission originates in pre-formed ground state aggregates of the pyrene derivatives incorporated into the polyion domain. Similar effects were observed when anionic polyelectrolytes, poly(styrene sulfonic), and poly(vinyl sulfonic) acids were added to cationic pyrene derivatives. The binding constants depend on the length of the aliphatic sidechain of the derivatives.     

Improving human health through understanding the complex structure of glucose polymers

Two highly branched glucose polymers with similar structures—starch and glycogen—have important relations to human health. Slowly digestible and resistant starches have desirable health benefits, including the prevention and alleviation of metabolic diseases and prevention of colon cancer. Glycogen is important in regulating the use of glucose in the body, and diabetic subjects have an anomaly in their glycogen structure compared with that in healthy subjects. This paper reviews the biosynthesis–structure–property relations of these polymers, showing that polymer characterization produces knowledge which can be useful in producing healthier foods and new drug targets aimed at improving glucose storage in diabetic patients. Examples include mathematical modeling to design starch with better nutritional values, the effects of amylose fine structures on starch digestibility, the structure of slowly digested starch collected from in vitro and in vivo digestion, and the mechanism of the formation of glycogen α particles from β particles in healthy subjects. A new method to overcome a current problem in the structural characterization of these polymers using field-flow fractionation is also given, through a technique to calibrate evaporative light scattering detection with starch.

Lichens as biomonitors for the determination of polycyclic aromatic hydrocarbons (PAHs) in Caracas Valley,Venezuela

Biomonitoring of PAH air pollution using lichens was carried out. Sixteen PAHs were studied in 11 locations along the valley of Caracas (Venezuela). The results of this work indicate that 14 of the 16 analysed PAHs were highly accumulated into the lichen thalli of Pyxine coralligera Malme. PAH levels in the samples revealed that the several volatile PAHs (naphthalene, acenaphtylene, acenaphtene, and fluoranthene) have the highest levels in the majority of the studied locations. The fluoranthene/pyrene and phenantrene/antracene ratios suggested that the major sources of PAHs are anthropogenic, mainly associated with gasoline and diesel combustion (pyrolytic) and unburnt oil derivates (petrogenic). The total PAH concentrations obtained in the present study were in the range of 0.24 to 9.08?µg/g, similar to those reported by other works in European and Asian cities.     

Synthesis of Densely Functionalised 5‐Halogen‐1,3‐oxazin‐2‐ones by Halogen‐Mediated Regioselective Cyclisation of N‐Cbz‐Protected Propargylic Amines: A Combined Experimental and Theoretical Study

A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I₂, Br₂ and Cl₂ as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed.     

Room Temperature Ionic Liquids in Asymmetric Hetero-Ene Type Reactions: Improving Organocatalyst Performance at Lower Temperatures

Room temperature ionic liquids (RTILs) have been widely used as (co)solvents in several catalytic processes modifying, in most of the cases, the catalyst activity and/or the selectivity for the studied reactions. However, there are just a few examples of their use in hydrogen bonding organocatalysis. In this paper, we show the positive effect of a set of imidazole-based ionic liquids ([bmim]BF₄ and [hmim]PF₆) in the enantioselective addition of formaldehyde tert-butylhydrazone to prochiral α-keto esters catalyzed by a sugar-based chiral thiourea. Reactions performed in the presence of low percentages of RTILs led to an increase of the catalyst activity, thereby making possible to work at lower temperatures. Thus, the chiral tert-butyl azomethyl tertiary alcohols could be obtained with moderate to good conversions and higher enantioselectivities for most of the studied substrates when using up to 30 vol% of [hmim]PF₆ as a cosolvent in processes performed in toluene.     

Large-scale Monte Carlo study of a realistic lattice model for Ga(1-x)MnxAs

Mn-doped GaAs is studied with a real-space Hamiltonian on an fcc lattice that reproduces the valence bands of undoped GaAs. Large-scale Monte Carlo (MC) simulations on a Cray XT3, using up to a thousand nodes, were needed. Spin-orbit interaction and the random distribution of the Mn ions are considered. The hopping amplitudes are functions of the GaAs Luttinger parameters. At the realistic coupling J approximately 1.2 eV the MC Curie temperature and magnetization curves agree with experiments for x = 8.5% annealed samples. Mn-doped GaSb and GaP are also briefly discussed.