Kinetic Buffers

This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH‐sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH–t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di‐copper(II) bistren complex in a single run, in a completely automatic experiment.     

Synthesis and characterization of sulfonated copolyethersulfones

The present article deals with the synthesis and characterization of some sulfonated copolyethersulfones. The synthetic approach differs from the post sulfonation approach traditionally reported in the literature. The synthetic procedure is based on the use of sulfonated monomers which are then reacted with previously synthesized telechelic hydoxy‐ended poly (ether sulpnone)s. Combining the MALDI‐TOF MS and ¹H NMR analyses, with SEC‐Viscometry and TGA measurements, we demonstrate a powerful tool for characterizing the chemical composition, end chains, degree of sulfonation (DS) and molecular mass distribution (MMD) of disulfonated poly(arylene ether‐sulfone) copolymers. The characterization techniques allowed to determine the exact nature of the copolymers synthesized and to reveal some interesting features about the reaction. DMA data show that the glass transition temperature of sulfonated copolymers with similar DS increase as raise their MMD. Copolymers with a DS of 10–11 mol % reach a T_g of 244–246 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3010–3023, 2010     

Biotites from tuffs located in Mendoza,Argentina, seen by Mössbauer spectroscopy

Several natural biotite samples were studied by M.E., electron microprobe and XRD. The M.E. parameters allow to group them as oxybiotites, normal biotites, chloritized biotites and muscovitized biotites. Mechanisms of oxybiotite formation and processes undergone by the rocks are discussed.     

Structural effects of lipophilic methotrexate conjugates on model phospholipid biomembranes

Lipophilic conjugates of the antitumor drug methotrexate (MTX) with lipoamino acids (LAAs) have been previously described as a tool to enhance MTX passive entrance into cells, overcoming a form of transport resistance which makes tumour cells insensitive to the antimetabolite. A knowledge of the mechanisms of interaction of such lipophilic derivatives with cell membranes could be useful for planning further lipophilic MTX derivatives with an optimal antitumour activity. To this aim, a calorimetric study was undertaken using a biomembrane model made from synthetic 1,2-dipalmitoyl-glycero-3-phosphocholine (DPPC) multilamellar liposomes. The effects of MTX and conjugates on the phase transition of liposomes were investigated using differential scanning calorimetry.

The interaction of pure MTX with the liposomes was limited to the outer part of the phospholipid bilayers, due to the polar nature of the drug. Conversely, its lipophilic conjugates showed a hydrophobic kind of interaction, perturbing the packing order of DPPC bilayers. In particular, a reduction of the enthalpy of transition from the gel to the liquid crystal phase of DPPC membranes was observed. Such an effect was related to the structure and mole fraction of the conjugates in the liposomes.

The antitumour activity of MTX conjugates was evaluated against cultures of a CCRF–CEM human leukemic T-cell line and a related MTX resistant sub-line. The in vitro cell growth inhibitory activity was higher for bis(tetradecyl) conjugates than for both the other shorter- and longer-chain derivatives. The biological effectiveness of the various MTX derivatives correlated very well with the thermotropic effects observed on the phase transition of DPPC biomembranes.     

Sulle formole per la composizione di più movimenti finiti

Rendiconti del Circolo Matematico di Palermo Series 1 -     

Exchange reactions occurring through active chain ends: Melt mixing of nylon 6 and polycarbonate

The chemical reactions occurring in the melt mixing of nylon6/polycarbonate (Ny6/PC) at 240°C were investigated. The reaction of equimolar Ny6/PC blends can be reconciled within the overall scheme of an exchange reaction occurring with the attack of active amino terminals on the inner carbonate groups. We have performed the synthesis of low molecular weight amino-terminated nylon 6 and the effect of the active amino terminal groups on the exchange kinetics was investigated. The exchange reaction yields sizeable amounts of copolymer, in fact after 75 min of melt mixing the (initially equimolar) blend contains 30 mol of unreacted PC and 70 mol of Ny6/PC copolymer (all the Ny6 was therefore incorporated in the copolymer). Trifluoroacetylation of nylon 6 was used to produce CHCl₃-soluble Ny6/PC copolymers, that could be analyzed by NMR. The NMR analysis yielded, beside the copolymer composition, evidence of the presence of urethane units interconnecting the Ny6 and PC blocks. The amount of urethane units increased with the reaction time, indicating a reduction of the block size as a function of the extent of exchange. Our study established the structure of the products formed, provided the materials balance of the process, and investigated some salient kinetic aspects. A thermal degradation study was also performed by thermogravimetry and direct pyrolysis mass spectrometry, to identify the products formed in the thermal treatment of the blends and to investigate the possible role of the inner amide groups in the intermolecular exchange reactions occurring between Ny6 and PC. Our results prove that these reactions occur above 300°C, and that only the cleavage of carbonate groups, by means of Ny6 amino end groups, is actually occurring at 240°C. © 1994 John Wiley & Sons, Inc.     

Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.     

Lempel–Ziv Factorization Using Less Time & Space

For 30 years the Lempel–Ziv factorization LZ _x of a string x = x[1..n] has been a fundamental data structure of string processing, especially valuable for string compression and for computing all the repetitions (runs) in x. Traditionally the standard method for computing LZ _x was based on Θ(n)-time (or, depending on the measure used, O(n log n)-time) processing of the suffix tree ST _x of x. Recently Abouelhoda et al. proposed an efficient Lempel–Ziv factorization algorithm based on an “enhanced” suffix array – that is, a suffix array SA _x together with supporting data structures, principally an “interval tree”. In this paper we introduce a collection of fast space-efficient algorithms for LZ factorization, also based on suffix arrays, that in theory as well as in many practical circumstances are superior to those previously proposed; one family out of this collection achieves true Θ(n)-time alphabet-independent processing in the worst case by avoiding tree structures altogether. The work of the first and third authors was supported in part by grants from the Natural Sciences & Engineering Research Council of Canada.