A simple method for the alkaline hydrolysis of esters

A very mild and rapid procedure for the efficient alkaline hydrolysis of esters in non-aqueous conditions has been developed, by the use of dichloromethane/methanol (9:1) as solvent. This method conveniently provides both carboxylic acids and alcohols from the corresponding esters and sodium hydroxide in a few minutes at room temperature. A plausible reaction mechanism is proposed.     

Über die Wirkung von Auxochromen in Flavyliumsalzen,I. 7-Hydroxy-flavyliumsalze

7-Hydroxy-flavylium salts absorb at longer wave lengths than the corresponding flavylium salts, yet auxochromes in 4′-position have a less bathochromic effect in the 7-hydroxy-flavylium series than in the flavylium series. As a result the absorption maxima converge. 4′-Dimethylamino derivatives show a convergence of 22 nm.     

Variation in sulfation pattern of galactosaminoglycan containing proteoglycans is associated with the development of uterine leiomyoma

The variations in sulfation patterns of glycosaminoglycans (GAGs) present in human normal myometrium and uterine leiomyoma were characterized following specific enzymic treatments and analysis by high-performance capillary electrophoresis (HPCE). Differences in the disaccharide composition of galactosaminoglycans (GalAGs) between normal myometrium and uterine leiomyoma were found. The results of this study suggest that the development of uterine leiomyoma is closely related not only to quantitative changes in the amount of GAGs but also in the sulfation of GalAGs. These differences may be attributed to increased synthesis of fibrotic connective tissue and deposition of collagen.     

157-nm Laser ablation of polymeric layers for fabrication of biomolecule microarrays

A new methodology for protein microarray fabrication is proposed based on the ablation of polymer film using laser at 157 nm (F₂). The polymer has been selected among others with the criterion of negligible protein adsorption. Improved results have been obtained by pretreatment of the polymer surface with an inert protein. The use of 157-nm laser radiation allowed very good depth control during the polymeric layer ablation process. In addition the importance of laser ablation at 157 nm is based on the fact that irradiated surfaces indicate limited chemical change due to the fact that laser ablation at 157 nm is only photochemical, thus avoiding excessive surface heating and damage. Results of protein microarray fabrication are presented to illustrate the viability of the proposed method.     

Beta-lactams as versatile synthons for homochiral ibotenate analogues with potential for activity at glutamate receptors

The activated beta-lactam aldehydes 37, 41 and 57 were synthesised. Aldehydes 37 and 57 proved to be more versatile substrates for our "ring switching" strategy to homochiral glutamate antagonists than the corresponding compounds in the pyroglutamate or 6-oxopipecolinate series had been. Substantial libraries of homochiral heteroaromatic glycine derivatives with potential for activity at specific glutamate receptor sub-types were prepared from these aldehydes. The aldehyde 41, containing an additional anion stabilising group, underwent a retro-aldol process under "ring switching" conditions.     

Spectrofluorimetric determination of magnesium in blood serium with calcein blue

Magnesium was determined in blood serum by fluorimetry with calcein blue (CB) in alkaline solution (0.01 M KOH). Four separate procedures for masking of iron, copper, zinc and calcium were applied. Complete masking was obtained with a mixture of ethylene glycol-O,O′-bis(2-aminoethyl)-N,N,N′,N′-tetraacetic acid, triethanolamine and triethylenetetramine. The mean value of magnesium in a 40-μl sample of quality control serum was within the appropriate limits of the reference sample. The effects of pH, masking agents and matrix of serum on the fluorescence of CB were investigated.     

Identification of Anionic Supramolecular Complexes of Sulfonamide Receptors with Cl<Superscript>−</Superscript>, NO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack>, Br<Superscript>−</Superscript>, and I<Superscript>−</Superscript> by APCI-MS

As part of a mass spectrometric investigation of the binding properties of sulfonamide anion receptors, an atmospheric pressure chemical ionization mass spectrometric (APCI-MS) method involving direct infusion followed by thermal desorption was employed for identification of anionic supramolecular complexes in dichloromethane (CH₂Cl₂). Specifically, the dansylamide derivative of tris(2-aminoethyl)amine (tren) (1), the chiral 1,3-benzenesulfonamide derivatives of (1R,2S)-(+)-cis-1-amino-2-indanol (2), and (R)-(+)-bornylamine, (3), were shown to bind halide and nitrate ions in the presence of (n−Bu)₄N⁺X⁻ (X⁻ = Cl⁻, NO₃⁻, Br⁻, I⁻). Solutions of receptors and anions in CH₂Cl₂ were combined to form the anionic supramolecular complexes, which were subsequently introduced into the mass spectrometer via direct infusion followed by thermal desorption. The anionic supramolecular complexes [M+X]⁻, (M=1–3, X⁻=Cl⁻, NO₃⁻, Br⁻, I⁻) were observed in negative mode APCI-MS along with the deprotonated receptors [M−H]⁻. Full ionization energy of the APCI corona pin (4.5 kV) was necessary for obtaining mass spectra with the best signal-to-noise ratios.     

Advanced MCMC methods for sampling on diffusion pathspace

The need to calibrate increasingly complex statistical models requires a persistent effort for further advances on available, computationally intensive Monte-Carlo methods. We study here an advanced version of familiar Markov-chain Monte-Carlo (MCMC) algorithms that sample from target distributions defined as change of measures from Gaussian laws on general Hilbert spaces. Such a model structure arises in several contexts: we focus here at the important class of statistical models driven by diffusion paths whence the Wiener process constitutes the reference Gaussian law. Particular emphasis is given on advanced Hybrid Monte-Carlo (HMC) which makes large, derivative-driven steps in the state space (in contrast with local-move Random-walk-type algorithms) with analytical and experimental results. We illustrate its computational advantages in various diffusion processes and observation regimes; examples include stochastic volatility and latent survival models. In contrast with their standard MCMC counterparts, the advanced versions have mesh-free mixing times, as these will not deteriorate upon refinement of the approximation of the inherently infinite-dimensional diffusion paths by finite-dimensional ones used in practice when applying the algorithms on a computer.     

Throughput Analysis of the Intermittent DCF for Opportunistic Spectrum Access

Recently, the opportunistic spectrum access (OSA) technologies have drawn a lot of the research community attention, because, by utilizing cognitive radio (CR) capabilities, they provide us with solutions to compensate for the spectrum underutilization. The MAC design is an important aspect of this on-going research. In this paper we study the performance of the distributed coordination function (DCF) in the OSA environment, which requires periodic intermissions to the MAC operation for spectrum scan procedures and opportunities identification. We present several modifications to the DCF that render it robust and operational in demanding environments of frequent spectrum scan procedures and low achievable transmission rates. We also present an analytical model for the throughput calculation of the resulted Intermittent DCF, which is based on the Bianchi’s Markov model and extends it so as to include the intermittent nature of the OSA environment. The proposed model is validated through simulations. A new parameter, controllable by the CR terminals, is used to optimize the throughput performance in realistic OSA scenarios. Using the presented analytical model we evaluate the performance of the Intermittent DCF under the effect of certain design parameters.     

Novel Functional Fullerene Materials: Fullerenes as Energy Acceptors

Summary.  Fullerene derivatives exhibit absorption throughout the UV/Vis region up to 750 nm. This feature is important for easy excitation. Once excited, fullerenes may become both electron and energy acceptors. The distinction between these two pathways depends strongly on the partner involved (donor) and on the conditions employed (solvent, etc.). Received June 23, 2000. Accepted July 7, 2000