New acyclic receptors containing pyridazine units. The influence of π-stacking on the selective transport of lipophilic phenethylamines

The synthesis of four new series of acyclic heteroaromatic receptors is described. They are built by two flexible polyether chains functionalised at their end with pyridazinone or methylpyridazine rings and connected by pyridine or benzene units. Their ability as carriers of lipophilic and hydrophilic phenethylamines and metallic cations has been evaluated. Transport rates show that, in general, these compounds are much more efficient carriers of lipophilic amines than of dopamine and Na⁺, K⁺ and Ca²⁺ ions. Their transport selectivities towards phenethylamine and homoveratrylamine are discussed on the basis of their structural features. Molecular modelling studies suggest that interaction of the aromatic moiety of the guest with the pyridazinone rings via double π-stacking, or with the pyridine ring by single π-stacking, should be responsible of their enhanced efficacy and selectivity in the transport of lipophilic phenethylamines.     

The use of arbitrarily primed polymerase chain reaction in cancer research

There is a great need for techniques that detect the genome alterations present in cancer cells. Here, we present a review of the arbitrarily primed polymerase chain reaction (AP-PCR), a genomic mutation detection method with some unique advantages: (i) It can detect most types of mutations that usually occur in tumors (except point mutations). (ii) It is especially useful to detect moderate gains in DNA, which most methods currently in use cannot detect. (iii) It allows detection and cloning of alterations in a single experiment. (iv) It is inexpensive and does not require special equipment. We discuss some characteristics of this method and review some of its achievements in cancer research.     

ITQ-16, a new zeolite family of the beta group with different proportions of polymorphs A,B and C

ITQ-16 is a new zeolite family formed by polymorphs A, B and C of the beta intergrowth in which the proportion of polymorph C can be controlled by changing the organic structure directing agent and/or by changing the Ge content of the synthesis gel; ITQ-16 can be synthesised either in fluoride or fluoride-free medium and Al can be introduced in the framework giving a material with very strong Br?nsted acidity.     

General and efficient methodology for the Suzuki-Miyaura reaction in technical grade 2-propanol

The reaction profile of a series of palladium-based catalysts was examined in the Suzuki-Miyaura reaction using technical grade 2-propanol as solvent and potassium t-butoxide as base. The results generally show high activity. The method allows for the coupling of electron-rich aryl chlorides with sterically hindered aryl boronic acids to produce tri-ortho-substituted biaryls in high yields using very mild conditions and short reaction times.     

Hydrogen peroxide photoproduction by the semicarbazide—tris(2,2′-bipyridine)ruthenium(II)—oxygen system

A light-driven system consisting of tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)₃²⁺) as the photosensitizer, semicarbazide as the electron donor and molecular oxygen as the electron acceptor has been employed for hydrogen peroxide production. The efficiency of this photosystem markedly depends on pH: while the peroxide yield is almost negligible at acid, neutral or slightly alkaline pH, it reaches significant values at high hydroxide concentrations, the initial rate of H₂O₂ formation drastically increasing from pH 12 to pH 14. In 1 M NaOH solutions containing Ru(bpy)₃²⁺ and semicarbazide at optimum concentrations, the number of catalytic cycles (or turnover number) undergone by the ruthenium complex over the complete course of the photochemical reaction is as high as 1.1 × 10⁴.

Spectrofluorometric and laser flash photolysis techniques were used to study the primary photochemical reactions involving the excited state of the ruthenium complex as well as the photochemically generated species Ru(bpy)₃³⁺ and Ru(bpy)₃⁺. It is proposed that at pH 14 a sequence of reactions leading to O₂ photoreduction by electrons from semicarbazide takes place, with the concomitant formation of H₂O₂; the excited state of Ru(bpy)₃²⁺ appears to react via oxidative quenching by oxygen rather than via reductive quenching by semicarbazide. At neutral pH, in contrast, there is no H₂O₂ formation owing to the fact that semicarbazide is unable to reduce (Ru(bpy)₃³⁺ to Ru(bpy)₃²⁺, although the photoexcited ruthenium complex is quenched equally by oxygen.     

Diazapolycyclic compounds—XIII : Reactions of diazaquinone adducts with N-bromosuccinimide

The action of N-bromosuccinimide on adducts obtained by Diels-Alder reaction of benzo(g)phthalazin-1,4-dione with substituted 1,3-butadienes is reported. Different addition or substitution products are formed depending on the solvent and reaction conditions. The stereochemistry of the most interesting among these compounds has been studied, and a possible mechanism for their formation is proposed.     

Determination of simazine, terbuthylazine, and their dealkylated chlorotriazine metabolites in soil using sonication microextraction and gas chromatography

A rapid analytical method is proposed for the determination of simazine, terbuthylazine, and their chloro dealkylated metabolites (simazine-desethyl, simazine-bisdesethyl, and terbuthylazine-desethyl) in soil. A sonication micromethod is presented for the extraction of -triazine herbicides and their metabolites. Final determination is by gas chromatography (GC) with nitrogen-phosphorus detection. The identity of all compounds was confirmed by GC with mass selective detection in the selected-ion monitoring mode. All chromatograms were very clean, without interfering peaks, and no cleanup was needed. The limits of detection were 1 pg for simazine-bisdesethyl; 5 pg for simazine, terbuthylazine, and terbuthylazine-desethyl; and 10 pg for simazine-desethyl. The limits of quantitation were 1, 5, and 10 ppb, respectively. Mean recoveries from fortified soils ranged from 76% for simazine-bisdesethyl to 102% for simazine-desethyl, with relative standard deviations of 3-6%.     

Comparison between electrochemical and optoelectrochemical impedance measurements for detection of DNA hybridization

The principles of the electrochemical and optoelectrochemical impedance measurements on bare electrolyte/dielectric/semiconductor structures are described. The analysis of the experimental curves allows access to several indications concerning the electrical behavior of such structures. The application of these techniques to follow the electrical behavior of structures modified with two biological systems was investigated. The antibody/antigen recognition did not change the surface charge and, therefore, did not affect the impedance curves with respect to the applied potential. By contrast, the hybridization of two complementary DNA strands on the surface of the structure induced a variation of flat band potential of the semiconductor leading to a shift of impedance curves along the potential axis. This means that it is possible to detect directly the DNA hybridization without the use of labeled probes. The use of light allows the surface to be probed locally. In the future, the application of this technique for direct detection of hybridization on DNA chips should be possible.