Pickering emulsion polymerization kinetics of styrene: Comparison of bare and surface modified SiO2 nanoparticles

A step towards the understanding of some mechanistic events occurring in the styrene Pickering emulsions, using a SiO₂ dispersion, is presented. Polymerizations at 80°C with different levels of a water soluble initiator were performed. The emulsion polymer content was ca. 15% with conversions close to 90%. With conversion and particle size measurements, the particle density was estimated for bare and surface modified SiO₂ particles. Then, the average number of radicals per particle was inferred, yielding a pseudo-bulk type polymerization. It was found that bare SiO₂ nanoparticles do not participate in the nucleation mechanism; however, they, along with the initiator, promote an enhanced oligomer coagulation. On the other hand, the hexadecyltrimethylammonium bromide modified SiO₂ nanoparticles do participate in the nucleation and coagulation mechanisms, yielding more stable and smaller poorly-covered polymer particles. This approach allowed untangling some events such as: particle nucleation, radical entry to particles, particle density, coagulation and vitreous and Trommsdorff effects.     

Batch Fermentation Model of Propionic Acid Production by Propionibacterium acidipropionici in Different Carbon Sources

Propionic acid (PA) is widely used as additive in animal feed and also in the manufacturing of cellulose-based plastics, herbicides, and perfumes. Salts of propionic acid are used as preservative in food. PA is mainly produced by chemical synthesis. Nowadays, PA production by fermentation of low-cost industrial wastes or renewable sources has been an interesting alternative. In the present investigation, PA production by Propionibacterium acidipropionici ATCC 4965 was studied using a basal medium with sugarcane molasses (BMSM), glycerol or lactate (BML) in small batch fermentation at 30 and 36 degrees C. Bacterial growth was carried out under low dissolved oxygen concentration and without pH control. Results indicated that P. acidipropionici produced more biomass in BMSM than in other media at 30 degrees C (7.55 g l(-1)) as well as at 36 degrees C (3.71 g l(-1)). PA and biomass production were higher at 30 degrees C than at 36 degrees C in all cases studied. The best productivity was obtained by using BML (0.113 g l(-1) h(-1)), although the yielding of this metabolite was higher when using glycerol as carbon source (0.724 g g(-1)) because there was no detection of acetic acid. By the way, when using the other two carbon sources, acetic acid emerged as an undesirable by-product for further PA purification.     

Preliminary test for nitrogen- and oxygen-containing groups in organic compounds

Summary Organic Compounds carrying groups containing both nitrogen and oxygen, such as nitro- and nitroso compounds, oximes, hydroxamic acids, azoxy compounds, and amine oxides yield nitrous acid when they are heated dry (pyrolysis). This product can be readily detected in the gas phase by theGriess nitrite reaction. This behavior provides a rapid preliminary test for members of these classes of compounds. Micro analytical limits of identification are readily obtained within the technique of spot test analysis.

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Zusammenfassung Organische Verbindungen mit Stickstoff- und sauerstoffhaltigen Atomgruppen, demnach Nitro- und Nitrosoverbindungen, Oxime, Hydroxamsäuren, Azoxy verbindungen und Aminoxyde spalten bei trockenem Erhitzen (Pyrolyse) salpetrige Säure ab, die in der Gasphase durch dieGriesssche Nitritreaktion empfindlich nachweisbar ist. Dieses Verhalten ermöglicht eine schnelle Vorprüfung auf Angehörige der genannten Verbindungsklassen. In der Technik der Tüpfelanalyse werden mikroanalytische Erfassungsgrenzen erreicht.

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Résumé Les combinaisons organiques porteuses d'un groupement azoté et oxygéné telles que les combinaisons nitrées et nitrosées, les oximes, les acides hydroxamiques, les composés azoxy et les oxydes d'aminés, libèrent de l'acide nitreux par chauffage à sec (pyrolyse); cet acide peut être identifié en phase gazeuse par la sensible réaction deGriess des nitrites. Ce comportement permet d'effectuer un essai préliminaire rapide sur les composés appartenant aux classes précédentes. Lorsqu'on met en oeuvre la technique de l'analyse à la touche, les limites de sensibilité atteintes permettent de travailler dans le domaine microanalytique.

     

Electromagnetic properties of theZ boson

Direct (nonresonant) 3-body decays of charmed mesons are calculated in chiral perturbation theory. The magnitudes of the 20 and 84 representations of the effective chiralSU(4)×SU(4) Lagrangian are determined from the measured 2-bodyD→Kπ rate. For decay modes which do not contain nonspectator contributions, the agreement of theoretical predictions with the data is satisfactory. Nevertheless, the large discrepancy between theory and experiment for decays which can proceed through theW-exchange orW-annihilation might imply the importance of nonperturbative corrections to the nonspectator diagram and the existence of final-state interactions.     

Piezoelectric textures of polycrystalline zinc selenide

The preliminary results of an investigation of the structure and electrophysical properties of CVD-grown polycrystalline ZnSe are reported. A weak multicomponent texture is observed which bears upon the piezoelectric effect, the characteristic features of the electric polarization, and the characteristic elastic oscillations of samples of regular shape. Zh. Tekh. Fiz. 69, 141–143 (February 1999)     

Characterization of isomers of oleuropein aglycon in olive oils by rapid‐resolution liquid chromatography coupled to electrospray time‐of‐flight and ion trap tandem mass spectrometry

In this work, rapid‐resolution liquid chromatography (RRLC) coupled to electrospray ionization time‐of‐flight mass spectrometry (ESI‐TOF‐MS) and ion trap multiple mass spectrometry (IT‐MSⁿ) has been applied to separate and characterize eleven isomers of oleuropein aglycon in fourteen Spanish extra‐virgin olive oils. After the extra‐virgin olive oil sample had been dissolved in hexane and cleaned up by a diol‐bonded phase solid‐phase extraction (SPE) cartridge, the eluting extract was resolved in methanol and analyzed on an Angilent 1200 system with a 4.6 × 150 mm, 1.8 µm Zorbax Eclipse plus C18 column. Mass spectrometry was carried out on a Bruker Daltonics microTOF mass spectrometer and a Bruker Daltonics ion trap mass spectrometer. The characterization of isomers of oleuropein aglycon was based on accurate mass data and the isotope function of characteristic fragment ions in the studied compounds by TOF‐MS, and the fragment ions were further confirmed by IT‐MSⁿ. The fragmentation pathway of oleuropein aglycon was successfully elucidated and all possible transformations among isomers of oleuropein aglycon were suggested. Copyright © 2008 John Wiley & Sons, Ltd.     

Co‐oxidation of ammonia and ethanol in supercritical water,part 2: Modeling demonstrates the importance of H2NNOx

A co‐oxidation model was constructed from available submechanisms for ammonia and ethanol oxidation. The ammonia submechanism validated for combustion at atmospheric pressure conditions was modified for the higher densities and lower temperatures (655–700°C) of supercritical water. The ethanol submechanism had previously been tested and validated at supercritical water conditions. The initial model poorly reproduced experimental ammonia conversion data and was not able to consistently match nitrous oxide production as a function of temperature over a range from 655–700°C at 246 bar. To improve model predictions, the low‐pressure NH₂ + NO_x submechanism was replaced with a submechanism that included the H₂NNO_x adduct species that are expected to be stabilized in the high‐pressure supercritical water environment. Thermochemical and kinetic parameters for the adduct species were estimated with quantum chemical calculations using Gaussian 98 with the CBS‐Q method. The explicit treatment of the H₂NNO_x adducts resulted in nitrous oxide yield predictions that correctly reproduced experimental trends. This work represents a vital first step in improving the understanding of ammonia oxidation in supercritical water. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 653–662, 2008     

Influence of the synthetic conditions on the structural diversity of extended manganese-oxalato-1,2-bis(4-pyridyl)ethylene systems

We report herein the synthesis and physicochemical characterization of eight new manganese-oxalato compounds with 1,2-bis(4-pyridyl)ethylene (bpe): {(Hbpe)(2)[Mn(2)(μ-ox)(3)]·～0.8(C(2)H(5)OH)·～0.4(H(2)O)}(n) (1), {[Mn(μ-ox)(μ-bpe)]·xH(2)O}(n) (2), [Mn(2)(μ-ox)(2)(μ-bpe)(bpe)(2)](n) (3), [Mn(μ-ox)(μ-bpe)](n) (4a and 4b), and {[Mn(4)(μ-ox)(3)(μ-bpe)(4)(H(2)O)(4)]·(X)(2)·mY}(n) with X = NO(3)(-) (5a), Br(-) (5b), and ClO(4)(-) (5c) and Y = solvation molecules. The appropriate selection of the synthetic conditions allowed us to control the crystal structure and to design extended 2D and 3D frameworks. Compound 1 is obtained at acid pH values and its crystal structure consists of stacked [Mn(2)(μ-ox)(3)](2-) layers with cationic Hbpe(+) molecules intercalated among them. Compound 2 was obtained at basic pH values with a manganese/bpe ratio of 1:1, and the resulting 3D structure consists of an interpenetrating framework in which metal-oxalato chains are bridged by bpe ligands, leading to a microporous network that hosts a variable number of water molecules (between 0 and 1) depending on the synthetic conditions. Compound 3, synthesized with a manganese/bpe ratio of 1:3, shows a 2D framework in which linear metal-oxalato chains are joined by bis-monodentate 1,2-bis(4-pyridyl)ethylene ligands. The thermal treatment of compound 3 permits the release of one of the bpe molecules, giving rise to two new 2D crystalline phases of formula [Mn(μ-ox)(μ-bpe)](n) (4a and 4b) depending on the heating rate. The open structures of 5a-5c were synthesized in a medium with a high concentration of nitrate, perchlorate, or bromide salts (potassium or sodium as cations). These anions behave as templating agents directing the crystal growing toward a cationic porous network, in which the anions placed in the voids and channels of the structure present high mobility, as inferred from the ionic exchange experiments. Variable-temperature magnetic susceptibility measurements show an overall antiferromagnetic behavior for all compounds, which are discussed in detail.     

The role of MAPK signal transduction pathways in the response to oxidative stress in the fungal pathogen Candida albicans: implications in virulence

In recent years, Mitogen-Activated Protein Kinase (MAPK) pathways have emerged as major regulators of cellular physiology. In the fungal pathogen Candida albicans, three different MAPK pathways have been characterized in the last years. The HOG pathway is mainly a stress response pathway that is activated in response to osmotic and oxidative stress and also participates regulating other pathways. The SVG pathway (or mediated by the Cek1 MAPK) is involved in cell wall formation under vegetative and filamentous growth, while the Mkc1-mediated pathway is involved in cell wall integrity. Oxidative stress is one of the types of stress that every fungal cell has to face during colonization of the host, where the cell encounters both hypoxia niches (i.e. gut) and high concentrations of reactive oxygen species (upon challenge with immune cells). Two pathways have been shown to be activated in response to oxidative stress: the HOG pathway and the MKC1-mediated pathway while the third, the Cek1 pathway is deactivated. The timing, kinetics, stimuli and functional responses generated upon oxidative stress differ among them; however, they have essential functional consequences that severely influence pathogenesis. MAPK pathways are, therefore, valuable targets to be explored in antifungal research.