The SCOPE dynamic model for emulsion polymerization II. Comparison with experiment and applications

Paper I provides the underlying theoretical framework for the SCOPE dynamic model of emulsion copolymerization. The present paper compares the model predictions for styrenemethyl methacrylate copolymerizations with experimental measurements made at a variety of polymerization conditions. The SCOPE model predicts conversion–time profiles reasonably well over wide ranges of initiator concentration, monomer concentration and monomer composition. In addition, the model accurately predicts number average molecular weights and copolymer compositions over the entire range of monomer composition. Like previous investigations of this system, the present study suggests that free radical desorption from polymer particles plays a dominant role on the copolymerization kinetics: Simple case II Smith-Ewart kinetics do not apply. The model for this system was applied to understand how changing reaction conditions could effect polymer properties such as particle size and molecular weight distributions. The power of the SCOPE model is illustrated by using it to predict conversion profiles, temperature profiles and copolymer properties for some large-scale versions of these recipes.     

Temporal dynamics and drivers of lake ecosystem metabolism using high resolution observations in a shallow,tropical, eutrophic lake (Laguna Lake,Philippines)

The physical, chemical, and biological dynamics under changing atmospheric conditions of Laguna Lake, Philippines were analyzed from intensive observations. Diel measurements were conducted for 48 continuous hours for both dry and wet tropical seasons in addition to fine resolution long-term monitoring. Results revealed significant vertical and diel variations of lake variables in spite of a shallow water depth (2.5 m) caused by the intense surface heating from solar irradiance (~800 W m^?2) and accentuated by the lake's high turbidity (16–32 ftu). Late afternoon land-lake breeze (~5–7 m s^?1) regularly breaks daytime thermal stratification, and convective cooling at night maintains isothermal condition until dawn of the next day. The stratified condition demonstrated a wind-driven, density-induced 2-layer current pattern with a windward moving epilimnion (~4 folds faster) and a compensating hypolimnetic flow in the general lake circulation direction. Laguna Lake was observed to have a dominating diel cycle but also undergoes significant seasonal limnological variations brought primarily by climate, hydrology, and its interaction with the adjacent sea. Significantly correlated variations of pH, chlorophyll-a and DO in the dry season were indicative of the higher biological activity associated with the intrusion of polluted waters from Metro Manila. The non-occurrence of thermal over-turn was observed to be regularly followed by bottom hypoxic conditions (2–4 mg L^?1), indicative of the eutrophic condition of the lake and the importance of diel wind-induced mixing in the bottom supply of DO. Laguna Lake was found to be predominantly net heterotrophic (GPP:R < 1, NEP < 0).     

Stereochemical Discrimination at Organic Crystal Surfaces 1: The Systems Serine/Threonine and Serine/Allothreonine

The stereoselective interactions in aqueous solution between the crystal faces of centrosymmetric (R,S) serine 1 and additives resolved and racemic threonine 2 and allothreonine 3 were studied by four independent techniques: change in crystal habit on growth, anisotropic distribution of occluded additive during the crystal growth, etch pit formation on partial dissolution and atom-atom potential energy calculations. The effects of the two diastereomers 2 and 3 are radically different due to differences in adsorption: threonine is adsorbed on the {011} crystal faces; the (R) enantiomer is adsorbed at, and eventually occluded through the (011) and (011) crystal faces replacing an (R) serine molecule. By symmetry, (S) threonine is adsorbed and occluded through the enantiotopic (011) and (011) faces replacing (S) serine. In contrast, (R) and (S) allothreonine are both adsorbed primarily at the (100) and (100) faces. The results indicate that the serine moiety of adsorbed threonine and allothreonine assume the same conformation and position as the substrate molecule. The additive is adsorbed only at specific sites such that the C_β-CH₃ groups emerge from the crystal surface. The observed effects lead in the case of threonine, but not allothreonine, to the assignment of its absolute configuration.     

Specific glucocorticoid receptor in the iris--ciliary body of the rabbit

The cytoplasm of the iris--ciliary body of the rabbit contains a receptor capable of specifically binding dexamethasone. This binding protein has a high affinity for dexamethasone (average KD = 2.0 X 10(-8) M), a low capacity (average 4.8 X 10(-13) mol of steroid bound per milligram of protein), and extreme heat sensitivity; it exhibits a pattern of competition virtually identical to that obtained with glucocorticoid receptors from other tissues and shows characteristic physicochemical behavior in various salt concentrations. The demonstration of a specific dexamethasone receptor in the iris--ciliary body provides the first direct biochemical evidence that these tissues may function as a target organ for glucocorticoids.     

Liposome-cell interaction: transfer and intracellular release of a trapped fluorescent marker

When small, unilamellar lipid vesicles containing a high concentration of the fluorescent dye 6-carboxyfluorescein are incubated with either frog retinas or human lymphocytes, fluroescence distributes widely throughout each cell. Since "self-quenching" largely prevents the dye from fluorescing as long as it remains sequestered in vesicles, it is clear that a considerable amount of dye is released from the vesicles and diluted into the much larger volume of the cell.     

Higher order need strengths as moderators of the job scope–job satisfaction relationship.

Questionnaire data on job characteristics, personality traits (Personality Research Form), and job satisfaction (Brayfield-Rothe Job Satisfaction Index) were obtained from 340 employees of a manufacturing organization. Moderated regression and subgroup analyses were performed to determine the extent to which 2 personality traits, need for achievement and need for autonomy, moderated the relationship between job scope and satisfaction with the work itself. The subgroup analysis showed no moderating effect for need for autonomy and moderating effects inconsistent with previous research and theory for need for achievement. Moderated regression showed no moderating effect for need for autonomy and a moderating effect of negligible practical importance for need for achievement. (37 ref) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Thermal analytical investigation of biopolymers and humic- and carbonaceous-based soil and sediment organic matter

Improved understanding of the physical, chemical, and thermodynamic properties of soil and sediment organic matter (SOM) is crucial in elucidating sorption mechanisms of hydrophobic organic compounds (HOCs) in soils and sediments. In this study, several thermoanalytical techniques, including thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), temperature-modulated differential scanning calorimetry (TMDSC), and thermal mechanical analysis (TMA) were applied to 13 different organic materials (three woods, two humic acids, three kerogens, and five black carbons) representing a spectrum of diagenetic and/or thermal histories. Second-order thermal transition temperatures (T(t)) were identified in most materials, where the highest observed T(t) values (typically characterized as glass transition temperatures (T(g were shown to closely relate to chemical characteristics of the organic samples as influenced by diagenetic or thermal alteration. Results further suggest a positive correlation between glass transition temperature and a defined diagenetic/thermal index, where humic-based SOM (e.g., humic and fulvic acids) possess lowertransition temperatures than more "mature" carbonaceous-based SOM (i.e., kerogens and black carbons). The observed higher thermal transition temperature of aliphatic-rich Green River shale kerogen (approximately 120 degrees C) relative to that of aromatic-rich humic acids suggests that a sole correlation of aromaticity to thermal transition temperature may be inappropriate.     

ECOWARM: News and information

ECOWARM: News and information     

A Comparison of Spawning,Harvested, and Die-Off Rainbow Smelt, Osmerus Mordax, in Eastern Lake Erie

Rainbow smelt were collected in the area of Long Point, Lake Erie from 1) a commercial trawler, 2) spawning runs in streams, and 3) die-offs along beaches. The parasite Glugea hertwigi was found to have no effects on the fecundity or condition of smelt. However, infested smelt grew more slowly than uninfested ones. The percentage of infested smelt in die-offs was not significantly higher than in the spawning stock, suggesting that the parasite was not the primary cause of the mortality. Growth, maximum age, and fecundity of smelt in the samples were lower than in most other smelt populations for which data are available. Since there are no data available for Lake Erie smelt prior to or during the development of the fishery, it is not possible to assess if the observed population structure is the result of exploitation. Sex ratio changes suggest that spawning smelt may remix with the harvested stock gradually throughout the summer.