Effects of an 8-bromodeoxyguanosine incorporation on the parallel quadruplex structure [d(TGGGT)]4

NMR, molecular dynamics and mechanics calculations, and CD spectroscopy were used to characterise three tetramolecular quadruplex complexes: [d(TG(Br)GGT)](4), [d(TGG(Br)GT)](4) and [d(TGGG(Br)T)](4), where G(Br) indicates an 8-bromoguanine residue. All three quadruplexes are characterised by a 4-fold symmetry with all strands parallel to each other and, differently to what has been observed for other parallel quadruplex structures, with a tetrad (formed by 8-Br-dGs) in a syn conformation. The whole of the data demonstrates that the replacement in turn of different dG residues with 8-Br-dG in the sequence 5[prime or minute]-TGGGT-3[prime or minute] affects the resulting structures in different ways, leading to different CD profiles and thermal stabilities. Particularly, [d(TG(Br)GGT)](4) and [d(TGG(Br)GT)](4) are more stable than the unmodified sequence, whereas [d(TGGG(Br)T)](4) is much less stable than the natural counterpart. The conformational features found in the three quadruplexes might, in principle, amplify the range of applicability of synthetic oligonucleotides as aptamers or catalysts, by providing novel structural motifs with different molecular recognition capabilities from those of native DNA sequences.     

Interaction of Alkyltin(IV) Compounds with Ligands of Interest in the Speciation of Natural fluids: Complexes of (CH3)2Sn2+ with Carboxylates

Complex formation by (CH₃)₂Sn²⁺ with acetate (ac), malonate (mal), 1,2,3-propane-tricarboxylate (tricarballylate, tca) and 1,2,3,4-butanetetracarboxylate (btc) ligands in aqueous solution is reported. The study has been performed by potentiometry ([H⁺]–glass electrode) at T=25 °C, and in the 0⩽I⩽1 mol dm⁻³ ionic strength range. In order to evaluate the salt effects on the formation constants of the complex species, and to contribute to the definition of the chemical speciation of diorganotin(IV) compounds in natural waters where carboxylic ligands are naturally present, interactions of NaCl (which is the major component of all natural fluids), with the components of the systems under investigation have also been considered. A model for the ionic strength dependence of the formation constant was used in order to calculate the values of thermodynamic constants, at infinite dilution, for all the proposed species, by considering hydrolytic species too. A relationship between the charges on the different ligands considered and the stabilities of the complex species formed is also discussed. © 1997 John Wiley & Sons, Ltd.     

Influence of water on the physical aging of poly(ethylene terephtalate)

Physical aging in polyethylene terephtalate (PET) has been studied on samples well characterized in terms of aging history and their content of water. This allows us to better understand the role played by water in the complex phenomenology of the physical aging in a hygroscopic material as PET. No appreciable changes in the thermal behavior in the sample aged in water at room temperature for one month were noted, while substantial changes were observed in samples aged in more severe conditions like 50°C under vacuum and 50°C in water for one month. The results are consistent with the formation of small regions in which segments of chains are closely packed.     

Recognition of the syndiotactic polypropylene polymorphs via dynamic-mechanical analysis

Three syndiotactic polypropylene samples were crystallized under different conditions in order to obtain different polymorphs. A first sample was crystallized at high temperature, obtaining the helical form I; a second was crystallized from the melt at 0°C for many days obtaining the trans-planar mesophase; a third sample was obtained by solvent induced crystallization followed by annaeling of the trans-planar mesophase, leading to a mixture of both the helical forms I and II. In the dynamic-mechanical analysis the helical form I showed only one peak of tan δ corresponding to the amorphous glass transition. The other polymorphs also showed this transition centered at about the same temperature. Beside the peak corresponding to the Tg, the trans-planar mesophase was characterized by a peak appearing at 70°C, and the helical form II by a peak at 100°C. These peaks, unambiguously associated to transitions of the different forms, can be considered a distinctive evidence for the polymorphs obtained in different processing conditions.     

Preconcentration and separation of haloacetic acids by ion chromatography

A comparative study was made of the chromatographic behaviour of five haloacetic acids (mono-, dibromoacetic and mono-, di-, trichloroacetic acids). The techniques investigated included reversed-phase ion interaction chromatography with UV detection, suppressed and non-suppressed anion-exchange chromatography. The systems are discussed studying the retention as a function of the mobile phase parameters and the stationary phases used (LiChrospher 100 RP-18, IonPac AS9, AS10 and AS11). A preconcentration step, performed on different substrates, namely LiChrolut-EN and activated vegetal carbon, has been optimized in order to reduce the method detection limits. Results obtained for drinking water samples are shown.     

Studies in organic mass spectrometry. Part 25. Benzyl ion formation in chemical ionisation (methane or isobutane) of some ortho-alkylhetero-substituted diphenylcarbinols

The behaviour of some ortho-alkylhetero-substituted diphenylcarbinols, including deuterium labelled derivatives, under chemical ionisation (methane or isobutane) conditions has been investigated. It has been determined that ortho-alkylhetero diphenylmethyl cations formed by water elimination from the protonated molecule undergo consecutive rearrangements which afford benzyl (or tropylium) ions previously observed for ortho-substituted diphenylcarbenium ions generated by electron ionisation. This reaction also occurs under low-energy collision conditions. Copyright 2000 John Wiley & Sons, Ltd.     

1,3-Dipolar cycloaddition of nitrones with α,β-unsaturated sulfones

C,N-Diphenyl nitrones react with substituted α,β-unsaturated phenylsulfones yielding isoxazolidinic cycloadducts whose structure and stereochemistry were assigned on the basis of ¹H and ¹³C nmr data. The ycloaddition regioselectivity is discussed in accordance with frontier orbital considerations.     

Transition entropies and mesomorphic behaviour of p-n-alkoxybenzyliden-p′-butoxyanilines

Calorimetric data on the mesogenic homologous series H₉C₄OC₆H₄NCHC₆H₄OC_nH_{2n + 1} are presented. Trends in the nematic-isotropic liquid transition temperatures, enthalpies and entropies are briefly discussed. A remarkable polymorphism is evidenced in several compounds. The importance of the thermal history of the samples in relation to their thermal behavior is shown.     

Thermodynamic parameters for the protonation of carboxylic acids in aqueous tetraethylammonium iodide solutions

The protonation constants of 21 carboxylic acids (formic, acetic, propionic, benzoic, phenoxyacetic, salicylic, oxalic, malonic, succinic, itaconic, malic, tartaric, oxydiacetic, thiodiacetic, thiodipropionic, phthalic, maleic, citric, 1,2,3-tricarboxylic, 1,2,4-tricarboxylic and 1,2,4,5-tetracarboxylic), have been determined potentiometrically, by pH-metric measurements, at several temperatures and ionic strengths, 5T55°C, 0<11 mol-dm^–3, using tetraethylammonium iodide as background salt. General equations for the dependence on ionic strength of thermodynamic parameters have been found. The statistical significance of results and the possibility of using a simple model for the thermodynamics of carboxylic acids protonation, is discussed.     

Engineering of layer-by-layer coated capsules with the prospect of materials for efficient and directed electron transfer

Intermolecular electron transfer is investigated in a dye-doped polyelectrolyte (PE) multilayer film. Hollow PE capsules, with a mean diameter of 2 microm, were prepared by stepwise adsorption of a pyrene (PY)-labeled polyanion and various polycations onto charged colloids and subsequent dissolution of the colloidal core. The high concentration of dye molecules within the capsule wall and the control of the medium polarity on a nanometer length scale are proposed to facilitate light-induced charge separation over distances of a few nanometers. In particular, a PY-labeled poly(styrene sulfonate) (PSS-PY) has been synthesized and used as polyanion for the polyelectrolyte capsule preparation. A polarity gradient across the wall of the PE shells is assumed to be achieved by adsorbing diverse polycations at different film positions. The high effective film area followed by high optical density of the PE capsule solution enables time-resolved optical spectroscopy. Using pulsed excited state absorption (ESA) the transient absorption peaks of the radical anion and cation state of pyrene were measured, respectively. In the presence of additional electron donor (or acceptor) molecules in the capsule solution the pyrene anion (cation) is observed in the ESA spectra, while both transient states are seen if no additional molecules are present. These results are interpreted as an electron transfer from pyrene to the donor (acceptor) molecule or between two pyrene molecules. An asymmetry of the electron donor and electron acceptor efficiency was observed when multilayer shells were used that are supposed to carry an internal polarity gradient.