Ion-exchange resins as stationary phase in reactive chromatography

Dynamic behavior of bothisothermal and non-isothermal single-column chromatographic reactors with an ion-exchange resin as the stationary phase was investigated. The reactor performance was interpreted by using results obtained when studying the effect of the resin properties on the equilibrium and kinetic phenomena occurring simultaneously in the reactor. Mathematical models were derived for each phenomenon and combined to simulate the chromatographic reactor. The phenomena studied includes phase equilibria in multicomponent liquid mixture¿ion-exchange resin systems, chemicalequilibrium in the presence of a resin catalyst, diffusion of liquids in gel-type and macroporous resins, and chemical reaction kinetics. Above all, attention was paid to the swelling behavior of the resins and how it affects the kinetic phenomena. Several poly(styrene-co-divinylbenzene) resins with different cross-link densities and internal porosities were used. Esterification of acetic acid with ethanol to produce ethyl acetate and water was used as a model reaction system. Choosing an ion-exchange resin with a low cross-link density is beneficial inthe case of the present reaction system: the amount of ethyl acetate as well the ethyl acetate to water mole ratio in the effluent stream increase with decreasing cross-link density. The enhanced performance of the reactor is mainly attributed to increasing reaction rate, which in turn originates from the phase equilibrium behavior of the system. Also mass transfer considerations favor the use ofresins with low cross-link density. The diffusion coefficients of liquids in the gel-type ion-exchange resins were found to fall rapidly when the extent of swelling became low. Glass transition of the polymer was not found to significantlyretard the diffusion in sulfonated PS¿DVB ion-exchange resins. It was also shown that non-isothermal operation of a chromatographic reactor could be used to significantly enhance the reactor performance. In the case of the exothermic modelreaction system and a near-adiabatic column, a positive thermal wave (higher temperature than in the initial state) was found to travel together with the reactive front. This further increased the conversion of the reactants. Diffusion-induced volume changes of the ion-exchange resins were studied in a flow-through cell. It was shown that describing the swelling and shrinking kinetics of the particles calls for a mass transfer model that explicitly includes the limited expansibility of the polymer network. A good description of the process was obtained by combining the generalized Maxwell-Stefan approach and an activity model that was derived from the thermodynamics of polymer solutions and gels. The swelling pressure in the resin phase was evaluated by using a non-Gaussian expression forthe polymer chain length distribution. Dimensional changes of the resin particles necessitate the use of non-standard mathematical tools for dynamic simulations. A transformed coordinate system, where the mass of the polymer was used as a spatial variable, was applied when simulating the chromatographic reactor columns as well as the swelling and shrinking kinetics of the resin particles. Shrinking of the particles in a column leads to formation of dead volume on top of the resin bed. In ordinary Eulerian coordinates, this results in a moving discontinuity that in turn causes numerical difficulties in the solution of the PDE system. The motion of the discontinuity was eliminated by spanning two calculation grids in the column that overlapped at the top of the resin bed. The reactive and non-reactive phase equilibrium data were correlated with a model derived from thethermodynamics of polymer solution and gels. The thermodynamic approach used inthis work is best suited at high degrees of swelling because the polymer matrixmay be in the glassy state when the extent of swelling is low.

Gas exchange of the umbu tree under semi-arid conditions

A study was carried out at Embrapa Semi-Árido, Petrolina-PE, Brazil, aiming to understand the gas exchange process of the umbu tree (Spondias tuberosa Arr. Cam.) in the dry and rainy seasons. Stomatal conductance, transpiration, photosynthesis and internal CO2 concentration were obtained with a portable infrared gas analyzer (IRGA). During the dry season the umbu tree showed a much lower stomatal conductance early in the morning, as soon as the vapor pressure deficit increased, apparently affecting CO2 assimilation more than transpiration. The highest values were detected around 6:00 am but decreased to the lowest points between 10:00 am and 2:00 pm. During the rainy season, however, stomatal conductance, transpiration and photosynthesis were significantly higher, reaching the highest values between 8:00 and 10:00 am and the lowest around 2:00 pm. It was also observed at 4:00 pm, mainly during the rainy season, an increase on these variables indicating that the umbu tree exhibits a two-picked daily course of gas exchange.

Water status and gas exchange of umbu plants (Spondias tuberosa Arr. Cam.) propagated by seeds and stem cuttings

The experiment was carried out at the Embrapa Semi-Árido, Petrolina-PE, Brazil, in order to study the physiological responses of umbu plants propagated by seeds and by stem cuttings under water stress conditions, based on leaf water potential and gas exchange measurements. Data were collected in one-year plants established in pots containing 30 kg of a sandy soil and submitted to twenty-day progressive soil water deficit. The evaluations were based on leaf water potential and gas exchange data collection using psychrometric chambers and a portable infra-red gas analyzer, respectively. Plants propagated by seeds maintained a significantly higher water potential, stomatal conductance, transpiration and photosynthesis under decreasing soil water availability. However, plants propagated by stem cuttings were unable to maintain a favorable internal water balance, reflecting negatively on stomatal conductance and leaf gas exchange. This fact is probably because umbu plants propagated by stem cuttings are not prone to formation of root tubers which are reservoirs for water and solutes. Thus, the establishing of umbu plants propagated by stem cuttings must be avoided in areas subjected to soil water deficit.

Charta öfver Svea och Göta Riken med Finland och Norland afritade i Stockholm år 1747 - [Yleisnäkymä - Overview]

Stockholm 1801

Wäg-karta ifrån Stockholm till Petersburg Itinéraire de Stockholm, à Petersbourg. Itinerary from Stockholm to Petersbourg - 1

S.l. 1835, E. Åkerland

Svea ock Göta Riken med Finland och Norland afritade i Stockholm år 1747 - [Översikten]

Stockholm : G. Biurman 1747

Otolith shape analysis as a tool for population discrimination of the white grunt (Haemulon plumieri) stock in the northern coast of the Yucatan Peninsula, Mexico

In this study, the population structure of the white grunt (Haemulon plumieri) from the northern coast of the Yucatan Peninsula was determined through an otolith shape analysis based on the samples collected in three locations: Celestún (N 20°49",W 90°25"), Dzilam (N 21°23", W 88°54") and Cancún (N 21°21",W 86°52"). The otolith outline was based on the elliptic Fourier descriptors, which indicated that the H. plumieri population in the northern coast of the Yucatan Peninsula is composed of three geographically delimited units (Celestún, Dzilam, and Cancún). Significant differences were observed in mean otolith shapes among all samples (PERMANOVA; F2, 99 = 11.20, P = 0.0002), and the subsequent pairwise comparisons showed that all samples were significantly differently from each other. Samples do not belong to a unique white grunt population, and results suggest that they might represent a structured population along the northern coast of the Yucatan Peninsula

Calendar anomalies in stock returns: Evidence from South America

This bachelor's thesis studies calendar anomalies in stock returns in five South American countries including Argentina, Brazil, Chile and Mexico. The analysis in done using regression analysis and the OLS- method.

Preparation of alpha-labeled aldehydes by base-catalyzed exchange reactions

A simple, efficient protocol for the preparation of α-labeled aldehydes based on H/D exchange catalyzed by 4-(N,N-dimethylamino)pyridine or Et3N is described. High chemical yields and ratios of isotope incorporation were obtained even when small amounts (1 mmol) of aldehyde were used.

Preparation of alpha-labeled aldehydes by base-catalyzed exchange reactions

A simple, efficient protocol for the preparation of α-labeled aldehydes based on H/D exchange catalyzed by 4-(N,N-dimethylamino)pyridine or Et3N is described. High chemical yields and ratios of isotope incorporation were obtained even when small amounts (1 mmol) of aldehyde were used.

AltitudeOmics : impaired pulmonary gas exchange efficiency and blunted ventilatory acclimatization in humans with patent foramen ovale after 16 days at 5,260 m.

A patent foramen ovale (PFO), present in ∼40% of the general population, is a potential source of right-to-left shunt that can impair pulmonary gas exchange efficiency [i.e., increase the alveolar-to-arterial Po2 difference (A-aDO2)]. Prior studies investigating human acclimatization to high-altitude with A-aDO2 as a key parameter have not investigated differences between subjects with (PFO+) or without a PFO (PFO-). We hypothesized that in PFO+ subjects A-aDO2 would not improve (i.e., decrease) after acclimatization to high altitude compared with PFO- subjects. Twenty-one (11 PFO+) healthy sea-level residents were studied at rest and during cycle ergometer exercise at the highest iso-workload achieved at sea level (SL), after acute transport to 5,260 m (ALT1), and again at 5,260 m after 16 days of high-altitude acclimatization (ALT16). In contrast to PFO- subjects, PFO+ subjects had 1) no improvement in A-aDO2 at rest and during exercise at ALT16 compared with ALT1, 2) no significant increase in resting alveolar ventilation, or alveolar Po2, at ALT16 compared with ALT1, and consequently had 3) an increased arterial Pco2 and decreased arterial Po2 and arterial O2 saturation at rest at ALT16. Furthermore, PFO+ subjects had an increased incidence of acute mountain sickness (AMS) at ALT1 concomitant with significantly lower peripheral O2 saturation (SpO2). These data suggest that PFO+ subjects have increased susceptibility to AMS when not taking prophylactic treatments, that right-to-left shunt through a PFO impairs pulmonary gas exchange efficiency even after acclimatization to high altitude, and that PFO+ subjects have blunted ventilatory acclimatization after 16 days at altitude compared with PFO- subjects.

A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids

A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form) in non-aqueous media. The anion loading of the AER (OH− form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.