Adsorption of stereoregular poly(methyl methacrylates) on γ-alumina: Spectroscopic analysis

ABSTRACTS: Three poly(methyl methacrylates) (PMMA) with a racemic fraction ranging from 0.25 to 0.91 have been adsorbed from a chloroform solution on γ-alumina and studied by diffuse reflectance infrared spectroscopy (DRIFT) and solid-state ¹³C NMR spectroscopy. From DRIFT spectra, it is seen that the fraction of carbonyl groups bonded to the surface goes from 0.29 for s-PMMA to 0.41 for i-PMMA, but there is a larger amount of s-PMMA retained on the surface (at any given solution concentration). NMR spectroscopy indicates, from shifts of the methylene and α-methyl carbon peaks (due to the γ-gauche effect), that the adsorption is accompanied by changes in conformation, with an increase in the number of trans conformers, particularly with i-PMMA. These results indicate that s-PMMA adsorbs on γ-alumina in a brush-like configuration, with a relatively small number of groups attached to the surface, and tails and loops sticking out of the surface, whereas i-PMMA adsorbs in a sheet-like configuration, with a greater number of interacting groups. In both cases, the adsorption is accompanied with an increase in the number of trans conformers as compared to the bulk conformation. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2985–2995, 1999     

A distributed Lagrange multiplier/fictitious domain method for flows around moving rigid bodies: Application to particulate flow

This article discusses the application of a Lagrange multiplier‐based fictitious domain method to the numerical simulation of incompressible viscous flow modeled by the Navier–Stokes equations around moving rigid bodies; the rigid body motions are due to hydrodynamical forces and gravity. The solution method combines finite element approximations, time discretization by operator splitting and conjugate gradient algorithms for the solution of the linearly constrained quadratic minimization problems coming from the splitting method. The study concludes with the presentation of numerical results concerning four test problems, namely the simulation of an incompressible viscous flow around a NACA0012 airfoil with a fixed center but free to rotate, then the sedimentation of 200 and 1008 cylinders in a two‐dimensional channel, and finally the sedimentation of two spherical balls in a rectangular cylinder. Copyright © 1999 John Wiley & Sons, Ltd.     

A Validated HPLC-PDA-HRMS Method to Investigate the Biological Stability and Metabolism of Antiparasitic Triterpenic Esters

Pentacyclic triterpenes (PTs) are commonly found in medicinal plants with well-known antiparasitic effects. Previous research on C-3 and C-27 triterpenic esters showed effective and selective in vitro antiparasitic activities and in vivo effectiveness by parenteral routes. The aim of this study was to determine triterpenic esters’ stability in different biological-like media and the main microsomal degradation products. An HPLC-PDA method was developed and validated to simultaneously analyze and quantify bioactive triterpenic esters in methanol (LOQ: 2.5 and 1.25–100 µg/mL) and plasma (LOQ: 5–125 µg/mL). Overall, both triterpenic esters showed a stable profile in aqueous and buffered solutions as well as in entire plasma, suggesting gaining access to the ester function is difficult for plasma enzymes. Conversely, after 1 h, 30% esters degradation in acidic media was observed with potential different hydrolysis mechanisms. C-3 (15 and 150 µM) and C-27 esters (150 µM) showed a relatively low hepatic microsomal metabolism (<23%) after 1 h, which was significantly higher in the lowest concentration of C-27 esters (15 µM) (>40% degradation). Metabolic HPLC-PDA-HRMS studies suggested hydrolysis, hydroxylation, dehydration, O-methylation, hydroxylation and/or the reduction of hydrolyzed derivatives, depending on the concentration and the position of the ester link. Further permeability and absorption studies are required to better define triterpenic esters pharmacokinetic and specific formulations designed to increase their oral bioavailability.     

Recent developments in rubber processing,leading to new applications such as the “green tyre”

Rubber articles derive most of their mechanical properties from the admixture of reinforcing fillers. Most commonly, carbon black is used as reinforcing filler. If silica is used instead, tyres made with such rubber compounds may exhibit a rolling resistance reduction by ca. 30%, which translates in substantial fuel savings of a car. Such silicas are far more difficult to mix with rubber than carbon black. Coupling agents are used as a surface modification of the filler to enhance compatibility with the polymer. Additionally they improve the ease of mixing with the rubber. The development of proper coupling agents combined with improved mixing techniques has contributed to the final break-through of the silicareinforced “Green Tyre”.     

Mass-selected reagent ion chemical ionization and multiple tandem mass spectrometry techniques in an ion trap mass spectrometer for structural analysis

Mass-selected reagent ion chemical ionization (CI) performed in an ion trap instrument is an efficient tool to investigate gas-phase ion reactivities and therefore to find out new and/or optimized applications for structural analysis. For instance, it was shown that the C₃H₆O^{+ .} (58 mass units) molecular ion originated from vinyl methyl ether (VME) should necessarily be used alone (i.e. unit-mass selected) to produce significant diagnostic-ions for double bond location in aliphatic alkenes. Regarding the assignment of epoxides, the previous NO⁺/CI method was adapted for an optimal use in the trap through isolation of NO⁺ cation from N₂O (instead of NO) plasma and production of the acylium diagnostic-ions via CID of [M − H]⁺ formed by NO⁺-induced hydride abstraction. New alkylation ion-products, e.g. RCH = O⁺-al , were also found to characterize isomeric epoxides as a result of either an initial electrophilic addition of the C₂H₅⁺ cation (with saturated epoxides) or a methyl-transfer from [VME]^{+ .} (with α,β-unsaturated epoxides). The multiple tandem mass spectrometry (MSⁿ) capabilities of the ion trap were essential to achieve reagent ion mass-selection, structural assignment of the diagnostic-ions, or to provide further selectivity. © 1997 John Wiley & Sons, Ltd.     

Paul Havrez und seine Benzolformel

The belgian chemist Paul Havrez (1838–1875) proposed two highly symmetrical, space-filling models for the benzene molecule, only a few months after Kekulé's seminal proposal of a cyclic benzene structure. One of these models is characterized by the revolutionary assumption of equal 3/2 bonds between all neighbouring carbon atoms, in sharp contrast to Kekulé's formula with alternating double and single bonds. With Considerable hind-sight, Havrez's model could be considered as a forerunner of the benzene structure with delocalized π bonds.     

Characterization of the surface of­bulk‐molded compounds

The automotive industry more and more frequently uses composite materials such as molded compounds (sheet‐molded compounds, SMC, or bulk‐molded compounds, BMC). Bonding is then the only way of assembling two pieces. Consequently, and in order tentatively to predict the adhesive behavior of such materials, it is necessary to have a good knowledge of their surface properties. Here, different complementary techniques of surface analysis allowed us, on the one hand, to reach this aim for BMCs prepared by compression molding and, on the other hand, to show the influence on the surface properties of the concentration and composition of the internal release agent added to the blend. The surface heterogeneity and the organic nature of the surface of the compounds are shown and no phase separation occurs there as in the bulk. Mold release agents remain in the surface layer and induce some acid–base character to the surface material which depends on the type of stearate introduced in the blend. Copyright © 1999 John Wiley & Sons, Ltd.     

The site of radical attack at the furan ring from MNDO calculations

The semi-empirical SCF MNDO method has been used to calculate the radical reactivities for each reaction site in some neutral furan molecules as the average of the HOMO and LUMO probabilities both in 2p_z atomic orbitals 1

1 SCF: Self-consistent field; MNDO: modified neglect of differential overlap; HOMO: highest occupied molecular orbital; LUMO: lowest unoccupied molecular orbital.

. The carbon atoms C⁵ and C² of of the furan ring are the most favoured sites except for the furan derivatives holding a double bond in the substituent group. Also the SOMO 2

2 SOMO: Single occupied molecular orbital.

probabilities of the radicals formed by addition of a hydrogen atom or a vinyl acetate model radical were calculated. Thus, once a radical is added to the C⁵ position the resulting radical can be partially localized on the carbon C². Furthermore, the enthalpy of reaction for several radicals was estimated by using the calculated heats of formation of the neutral furan molecules and their radicals. The radical addition to the carbon C ⁵ resulted in the most exothermic reaction in comparison with other reaction sites of the molecule. However, no correlation was found between the calculated enthalpies and the degradative-transfer kinetic constants experimentally determined for the radical polymerization of vinyl acetate in the presence of the furan compounds under study.     

The state of water in swollen polymers

It is shown that by low frequency measurements in hydrophilic polymers only one state of water is observed. Water behave as a classical plasticizer and ice melting in polymer is similar to ice melting in binary simple mixture. The non crystallizable water in these systems is explained by the Tg regulation effect. In oriented swollen polymers, only one state of water is observed in the time scale ∼ 1/ω_q = 10⁻⁵ s by deuterium NMR. This technique gives information on the mean orientation of D₂O molecules in the oriented polymer and on the fraction of mobile water molecules. The concept of bound and unbound water is not relevant for explaining the DSC and D-NMR results.