Synthesis and hydrophobic association of poly(N,N‐dimethylacrylamide) end‐functionalized with perfluorocarbon and hydrocarbon groups

Polydimethylacrylamides (PDMAs) end‐functionalized with hydrophobic groups were synthesized by the reaction of cesium salts of one‐ or two‐ended living PDMA anion with octadecanoyl and perfluorooctanoyl chlorides and with α‐phenylacrylate monomers containing an octadecyl group attached via oligooxyethylene spacers to the acrylate functionality. Size exclusion chromatography or NMR studies indicated that the end functionalizations were nearly quantitative. Reduced viscosity measurements were consistent with predominantly dimeric association of the perfluorooctanoyl‐end‐functionalized PDMAs. The association of the two‐ended, perfluorooctanoyl‐ and octadecanoyl‐functionalized polymers was more extensive and consistent with pairwise association. Furthermore, the presence of oligoethylene oxide spacers between the octadecyl and α‐phenylacrylate groups greatly enhanced the hydrophobic association of bis(octadecyl)‐end‐functionalized PDMA. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1403–1418, 2001     

Selectivity optimization for the capillary gas chromatographic analysis of bacterial cellular fatty acids

Summary The importance of selectivity in the capillary gas chromatographic analysis of the cellular fatty acids of micro-organisms is underestimated. The analysis on apolar silicone phases can lead to erratic elucidation of the fatty acid structure. Qualitative errors have been detected in commercially available standards on which computer matching identification techniques are based. Using highly polar capillary columns of the cyanopropyl silicone type, the errors could be elucidated. The exact identification of the hydrolysis products of bacteria is a must for chemotaxonomic studies applying chromatographic techniques. The fatty acid methyl ester profiles can also contain other chemical components which are very important taxonomic markers. Fatty aldehydes, for example, are main components in someClostridium species. Fractionation techniques are described for selective enrichment of fatty aldehydes and hydroxy fatty acids.Dedicated to Prof. Dr. A Liberti on the occasion of his 70th birthday     

Use of poly(ethylene terephtalate) film bag to sample and remove humidity from atmosphere containing volatile organic compounds

Nalophan bags made from poly(ethylene terephtalate) film are often used to collect odorous gases. In this paper, the sample water removal method, based on humidity diffusion through the sample bag film, was applied using Nalophan bags and Tedlar bags to sample volatile organic compounds (VOCs) at low concentration (10 microg/m(3)). The removal of water with Nalophan bags enabled a reduction in relative humidity (RH) in a 10-L air sample from 80% to 20% in 2h at 20 degrees C. The use of Nalophan bags for the removal of water did not involve significant VOC loss among the 11 compounds studied.     

Aging effect on the mechanical properties of hybrid gels

Sol-gel derived unsupported films and thin rods have been obtained from co-hydrolysis of triethoxysilane and methyldiethoxysilane. The materials are flexible, dense and transparent. Films and rods have been aged for different periods of time in air at room temperature. The elastic modulus has been measured by means of tensile or flexural tests. Measurements showed an increase of elastic modulus with aging time and showed different values for films and rods. The observed evolution of mechanical properties has been related to a corresponding structural modification as highlighted mainly by MAS-NMR studies. Analyses pointed out the crucial role of condensation processes and showed that the stiffness increase arises from the formation of relatively few bonds which link and constrain pre-existing mobile network regions.     

A fluorescence displacement assay for antidepressant drug discovery based on ligand-conjugated quantum dots

The serotonin (5-hydroxytryptamine, 5-HT) transporter (SERT) protein plays a central role in terminating 5-HT neurotransmission and is the most important therapeutic target for the treatment of major depression and anxiety disorders. We report an innovative, versatile, and target-selective quantum dot (QD) labeling approach for SERT in single Xenopus oocytes that can be adopted as a drug-screening platform. Our labeling approach employs a custom-made, QD-tagged indoleamine derivative ligand, IDT318, that is structurally similar to 5-HT and accesses the primary binding site with enhanced human SERT selectivity. Incubating QD-labeled oocytes with paroxetine (Paxil), a high-affinity SERT-specific inhibitor, showed a concentration- and time-dependent decrease in QD fluorescence, demonstrating the utility of our approach for the identification of SERT modulators. Furthermore, with the development of ligands aimed at other pharmacologically relevant targets, our approach may potentially form the basis for a multitarget drug discovery platform.     

Evaluation of automated sample preparation, retention time locked gas chromatography-mass spectrometry and data analysis methods for the metabolomic study of Arabidopsis species

In this paper, automated sample preparation, retention time locked gas chromatography-mass spectrometry (GC-MS) and data analysis methods for the metabolomics study were evaluated. A miniaturized and automated derivatisation method using sequential oximation and silylation was applied to a polar extract of 4 types (2 types×2 ages) of Arabidopsis thaliana, a popular model organism often used in plant sciences and genetics. Automation of the derivatisation process offers excellent repeatability, and the time between sample preparation and analysis was short and constant, reducing artifact formation. Retention time locked (RTL) gas chromatography-mass spectrometry was used, resulting in reproducible retention times and GC-MS profiles. Two approaches were used for data analysis. XCMS followed by principal component analysis (approach 1) and AMDIS deconvolution combined with a commercially available program (Mass Profiler Professional) followed by principal component analysis (approach 2) were compared. Several features that were up- or down-regulated in the different types were detected.     

Supramolecular chemistry of half-sandwich organometallic building blocks based on RuCl2(p-cymene)Ph2PCH2Y

A new series of neutral organometallic building blocks based on piano-stool ruthenium(II) complexes, RuCl₂(p-cymene)Ph₂PCH₂Y [Y = -NHC₆H₄(2-CO₂H) (2a), -NHC₆H₄(3-CO₂H) (2b), -NHC₆H₃(3-CO₂H)(6-OCH₃) (2c), -NHC₆H₄(4-CO₂H) (2d), -NHC₆H₃(2-CO₂H)(4-OH) (2e), -NHC₆H₃(3-OH)(4-CO₂H) (2f), -NHC₆H₃(2-CO₂H)(5-CO₂H) (2g) and -OH (2h)], were synthesised in high yields (>88%) from {RuCl₂(p-cymene)}₂ and the appropriate phosphines 1a-1h. The new tertiary phosphine 1b was prepared by Mannich condensation of NH₂C₆H₄(3-CO₂H) with Ph₂PCH₂OH in MeOH. Solution NMR (³¹P{¹H}, ¹H), FT-IR and microanalytical data are in full agreement with the proposed structures. Single crystal X-ray studies confirm that, in each case, compounds 2a, 2b and 2d-2h have piano-stool arrangements with typical Ru-P, Ru-Cl and Ru-C_centroid bond lengths. From our crystallographic studies, factors that influence the supramolecular assemblies of these ruthenium(II) complexes include: (i) the type of functional group present, (ii) the geometric disposition of the -N(H)CH₂PPh₂, -CO₂H and -OH groups around the central benzene scaffold, and (iii) the solvents used in the recrystallisations. Hence in isomers 2a and 2b, molecules are associated into head-to-tail dimer pairs through classical intermolecular O-H?O hydrogen bonding. This feature is also observed in isomer 2d but dimer pairs are further associated to give a 1-D chain through assisted intermolecular N-H?Cl hydrogen bonding. The additional 4-hydroxo group in 2e promotes a ladder arrangement via intermolecular O-H?O and O-H?Cl hydrogen bonding. In contrast the isomeric compound 2f does not show head-to-tail O-H?O hydrogen bonding but instead O-H?Cl and N-H?O intermolecular hydrogen bonding is observed. Depending on the choice of solvent (MeOH or DMSO), 2g forms extended networks based on chains (2g · DMSO · 1.5MeOH) or tapes (2g · 3MeOH). In 2h, a single intramolecular O-H?Cl hydrogen bond is observed for each independent molecule. The X-ray structure of one representative tertiary phosphine, 1f, has also been determined.     

Quantitative sphingosine measurement as a surrogate for total ceramide concentration—preclinical and potential translational applications

Biomarkers are an increasingly important constituent of the drug development process, offering the potential of increased efficiency through reduced compound attrition and earlier proof of mechanism and/or efficacy. Assays developed for compound screening that can be directly translated for clinical trials are especially valuable, but their successful adoption requires a careful balance between assay performance and implementation costs. One such ‘fit‐for‐purpose’ biomarker assay, the indirect measurement of pharmacological modulation of sphingolipid biosynthesis and disposition, is presented here. Among spingolipids, numerous ceramide species are readily detectable in different lipoprotein fractions of mammalian plasma, but their parallel quantification can be prohibitively expensive and time consuming. Ceramides differ in their fatty acid moiety, which is readily removed by hydrolysis, yielding a common sphingosine derivative, the measurement of which serves as an indicator of total ceramide. When followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for detection, robust analyte quantification becomes relatively straightforward. The practical utility of a method developed to be fit for the purpose of rapidly and quantitatively measuring treatment‐induced variations in total ceramide from hamster plasma and individual lipoprotein fractions is described. With a linear calibration range from 0.003 to 33.4 μm sphingosine, precision and accuracy error in plasma‐based quality controls spiked with ceramides was less than 15%. The specificity of the assay for ceramides was also assessed. The simplicity of the method would allow for its potential translation to other preclinical species, as well as for clinical applications in later‐stage drug development. Copyright © 2009 John Wiley & Sons, Ltd.     

Dialkylzinc-assisted alkynylation of nitrones

[reaction: see text]. Reaction of nitrones with terminal alkynes takes place readily in the presence of a substoichiometric amount of diethylzinc in toluene, affording N-propargyl-hydroxylamines in excellent yields and purity.     

Trimethoxysilylpolymethacrylate as new material for stone conservation. Porosimetric and colorimetric investigations

Aimed to obtain new materials for the conservation of stone substrates, we report here on the synthesis of a polymer which has been obtained by inducing polymerization on a methacrylate monomer functionalized by alchoxysilane groups. Two lithotypes, the Comiso calcarenite and Mistretta quartzite, stones largely used in artworks of north-eastern Sicily, were treated with the above polymer and its conserving efficacy evaluated in terms of porosimetric features, hydric properties and appearance. The collected data were compared to those provided, under the same experimental conditions, by an ethylmethacrylate/methylmethacrylate copolymer and an alkylalchoxysilane, products widely employed in the protection of stones. Experiments aimed to test the durability of the above polymer against UV artificial ageing are also reported.