Diffusivity of small molecules in polymers: Carboxylic acids in polystyrene

Gravimetry was used to study the diffusion of a homologous series of linear carboxylic acids (C_n, with n = 2, 6–16) in amorphous polystyrene at temperatures from 35 °C to 165 °C, that is, both below and above the polymer glass transition temperature of 100 °C. All the mass uptake results are well described by a simple Fickian model (for t < t_1/2) and were used to calculate the corresponding diffusion coefficients using the thin-film approximation. Acetic acid exhibits a peculiar diffusion rate: its diffusion coefficients in polystyrene do not follow the same trend of all the remaining acids, being smaller than those of hexanoic acid at the same temperatures. Polystyrene swells at a higher rate in hexanoic and octanoic acids than in acetic acid, at the same temperature. This peculiarity is confirmed using NMR spectroscopy for acetic and hexanoic acids. For all the carboxylic acids considered, the temperature dependence of the diffusion coefficients is non-Arrhenius in character. For each liquid penetrant, its log(D) increases linearly with the decrease in liquid viscosity associated with an increase in temperature. Plots of log(n²D) versus n suggest that higher-n carboxylic acids diffuse through a reptation-like mechanism at higher temperatures.     

Drag Reduction by Wormlike Micelles of a Biodegradable and Non-Biodegradable Surfactants

This study describes the effects of wormlike micelles formed by the commercial surfactants tallowalkylamidopropyl dimethylamine oxide (Aromox APA-TW) and oleyl methyl bis(2-hydroxyethyl) ammonium chloride (Ethoquad O/12) as drag reducers. Ethoquad O/12 is immune to degradation by heat and microorganisms. Conversely, Aromox APA-TW is biodegradable in the environment, and its susceptibility to heat-induced degradation was previously assessed. This work considers the effects of temperature, salt, and time on the drag-reduction capacity (in different Reynolds number) of wormlike micelles of these two surfactants. Wormlike micelles formed by Aromox APA-TW are able to reduce drag at higher temperatures compared to wormlike micelles formed by Ethoquad O/12. However, Aromox APA-TW can degrade after being heated to 80 °C and also after storage of the wormlike micelle solutions. Ethoquad O/12 does not undergo degradation after being heated or stored. These surfactants have the potential to be used as additives in industrial operations, as the wormlike micelles formed are able to reduce drag in systems with long pumping distances or recirculation, even in solutions with high salt concentrations (brine) and high temperatures.     

Kinetics of Soybean Oil Hydrolysis on Niobium Catalysts

The catalytic hydrolysis of soybean oil was used as an alternative for the production of monoglycerides (MG) and diglycerides (DG). The reactions were conducted in a stainless-steel tubular reactor in the temperature range of 240–290 °C, on niobium phosphate (NBP) and niobium oxide (NBO) as catalysts. In the hydrolysis reactions at 270 °C, the maximum selectivities of the products of interest were obtained at 22 % MG and 48 % DG for the reaction with NBP, and 7 % MG and 33 % DG with NBO, for 59 % and 36 % of triglyceride conversion in 10 min, respectively. The proposed kinetic model presented a good fit of the theoretical model with the experimental data, showing that the previous hypotheses considered for the mechanism development are suitable for describing the kinetics of soybean oil hydrolysis.     

The Crosstalk of Adipose-Derived Stem Cells (ADSC), Oxidative Stress,and Inflammation in Protective and Adaptive Responses

The potential use of stem cell-based therapies for the repair and regeneration of various tissues and organs is a major goal in repair medicine. Stem cells are classified by their potential to differentiate into functional cells. Compared with other sources, adipose-derived stem cells (ADSCs) have the advantage of being abundant and easy to obtain. ADSCs are considered to be tools for replacing, repairing, and regenerating dead or damaged cells. The capacity of ADSCs to maintain their properties depends on the balance of complex signals in their microenvironment. Their properties and the associated outcomes are in part regulated by reactive oxygen species, which mediate the oxidation-reduction state of cells as a secondary messenger. ADSC therapy has demonstrated beneficial effects, suggesting that secreted factors may provide protection. There is evidence that ADSCs secrete a number of cytokines, growth factors, and antioxidant factors into their microenvironment, thus regulating intracellular signaling pathways in neighboring cells. In this review, we introduce the roles of ADSCs in the protection of cells by modulating inflammation and immunity, and we develop their potential therapeutic properties.     

Surface Modification of Polydimethylsiloxane via Combined Aminolysis and Alcoholysis Generating Cell Adhesive and Antifouling Properties

Polydimethylsiloxane (PDMS) is an elastomeric polymer frequently used as implant material, for flexible tubing and in microfluidic devices. The pronounced hydrophobic surface of this unique material impedes many applications where a good wetting behavior is required. Consequentially, various ways of surface modifications have been used to introduce new properties. Plasma treatment is the most popular technique in this respect, but is not generally applicable, especially if hardly accessible surfaces are to be modified. A novel wet-chemistry-based modification scheme yielding an amino-functionalized PDMS surface using a combined alcoholysis/aminolysis reaction is presented. Biological applications are exemplified by the conjugation of the RGD peptide, or polyethylene glycol (PEG) and heparin, yielding surfaces with cell-adhesive or nonthrombogenic properties, respectively. The effect of subsequent conjugation with an adhesive peptide is tested in cell culture. Additionally, two antifouling surfaces generated by coupling heparin and polyethylene glycol respectively are shown to improve the materials resistance to platelet adhesion drastically while simultaneously preventing hydrophobic recovery of the PDMS surface. The findings provide a versatile means of surface functionalization of PDMS substrates and is suitable for many biomedical applications.     

A non-antibacterial oxazolidinone derivative that inhibits epithelial cell sheet migration

We have developed a high-throughput assay for screening chemical libraries for compounds that affect cell sheet migration during wound closure in epithelial cell monolayers. By using this assay, we have discovered a new inhibitor of cell sheet migration. This compound (UIC-1005) is a 3,4-disubstituted oxazolidinone that bears an electrophilic alpha,beta-unsaturated N-acyl group required for activity. UIC-1005 also inhibits growth in an epithelial cell proliferation assay. The molecule does not display general toxicity at concentrations at which it potently inhibits cell sheet migration and growth. Unlike certain 3,5-disubstituted oxazolidinones, it exhibits no antibacterial activity. UIC-1005 therefore represents a new class of bioactive oxazolidinone derivative that may prove useful as a probe for signaling pathways leading to cell motility.     

Comparison of a contactor catalytic membrane reactor with a conventional reactor: example of wet air oxidation

A wet air oxidation reaction was carried out in a gas/liquid catalytic membrane reactor of the contactor type. The oxidation of formic acid was used as a model reaction. The mesoporous top-layer of a ceramic tubular membrane was used as catalyst (Pt) support, and was placed at the interface of the gas (air) and liquid (HCOOH solution) phases.

A similar reaction was carried out in a conventional batch reactor, using a steering rate high enough to avoid gas-diffusion limitations, and exactly identical conditions than for the CMR (amount of catalyst, pressure, etc.). At room temperature, the CMR showed an initial activity three to six times higher than the conventional reactor. This activity increase was attributed to an easier oxygen access to the catalytic sites. Nevertheless, the catalytic membrane gradually deactivated after a few hours of operation. Different deactivation mechanisms are presented.     

Structural Diversity and Defensive Properties of Norditerpenoid Alkaloids

We have tested the insect antifeedant and toxic activity of 43 norditerpenoid alkaloids on Spodoptera littoralis and Leptinotarsa decemlineata including eserine (physostigmine), anabasine, and atropine. Antifeedant effects of the test compounds were structure- and species-dependent. The most active antifeedants to L. decemlineata were 1,14-diacetylcardiopetaline (9) and 18-hydroxy- 14-O-methylgadesine (33), followed by 8-O-methylconsolarine (12), 14-O-acetyldelectinine (27), karakoline (7), cardiopetaline (8), 18-O-demethylpubescenine (13), 14-O-acetyldeltatsine (18), takaosamine (21), ajadine (24), and 8-O-methylcolumbianine (6) (EC50 < 1 microg/cm2). This insect showed a moderate response to atropine. S. littoralis had the strongest antifeedant response to 24, 18, 14-O-acetyldelcosine (19), and delphatine (29) (EC50 < 3 microg/cm2). None of the model substances affected the feeding behavior of this insect. The most toxic compound to L. decemlineata was aconitine (1), followed by cardiopetalidine (10) (% mortality > 60), 14-deacetylpubescenine (14), 18-O-benzoyl-18-O-demethyl-14-O-deacetylpubescenine (17), 14-O-acetyldelcosine (19), 14-deacetylajadine (25) and methyllycaconitine (30) (% mortality > 45). Orally injected S. littoralis larvae were negatively affected by 1, cardiopetaline (8), 10, 1,14-O-acetylcardiopetalidina (11), 12, 14, 1,18-O-diacetyl-19-oxo-gigactonine (41), olivimine (43), and eserine in varying degrees. Their antifeedant or insecticidal potencies did not parallel their reported nAChR binding activity, but did correlate with the agonist/antagonist insecticidal/antifeedant model proposed for nicotininc insecticides. A few compounds [14, tuguaconitine (38), 14-demethyldelboxine (40), 19, dehydrodelsoline (36), 18-O-demethylpubescenine (13), 41, 9, and delcosine (23)] had selective cytotoxic effects to ward insect-derived Sf9 cells. None were cytotoxic to mammalian CHO cells and none increased Trypanosoma cruzi mortality. The selective cytotoxic effects of some structures indicate that they can act on biological targets other than neuroreceptors.     

Impact fracture behavior of ethylene ionomer and structural change after stretching

We carried out tensile impact test and very low speed tensile test on ethylene‐based Ionomers (E/15wt %MAA) to clarify the relation between impact toughness and high‐ordered structure. We also studied the changes in high‐ordered structure under deformation by observing Differential Scanning Calorimetory (DSC) and Small‐Angle X‐ray Scattering (SAXS) of fractured surface. Na Ionomers showed ductile fracture in both high speed tensile impact (3 m/s) and very low speed tensile (2 mm/min). The disappearance of secondary melting point (Ti) in Na Ionomers was due to the destruction of ordered structure surrounding the ionic aggregate. Similar behavior was observed in 60% (or less) neutralized Zn Ionomers. However, 80% neutralized Zn Ionomer showed brittle failure in high‐speed tensile impact, and Ti did not disappear. SAXS studies of Na and Zn Ionomers after fracture, show no change both after molding (no aging) and after aging. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1712–1720, 2001