On the role of hydrophilicity and hydrophobicity in aqueous heterophase polymerization

This paper reports on experimental results of aqueous heterophase polymerizations with monomers of quite different solubility in water ranging from the water-soluble 2-hydroxyethyl methacrylate to lauryl methacrylate with solubility in water of only about 10⁻⁴ mM. A calorimetric study revealed the strong influence of both the hydrophilicity of the monomer and the stirrer speed on the rate of polymerization in the absence of surfactants. In order to obtain maximum latex yield and high efficiency (which is a measure considering colloidal properties, polymerization recipe, and polymerization parameters) the initiator-surfactant combination must be properly chosen in dependence on the hydrophilicity of the monomer. Results are presented for sodium alkyl sulfates or disodium-N-stearoyl-l-glutamate as surfactant and potassium peroxodisulfate, or poly(ethylene glycol)-azo- compounds, or 2,2′-azobis(N-2′-methylpropanoyl-2-amino-alkyl-1)-sulfonates as initiators.     

Structural control in radical polymerization with 1,1 diphenylethylene: 2. Behavior of MMA-DPE copolymer in radical polymerization

Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only.     

Comparing emulsion polymerization of methacrylate-monomers with different hydrophilicity

A comprehensive experimental study concerning the influence of various types of initiator-emulsifier systems on emulsion polymerization of methacrylate monomers (2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA) and butyl methacrylate (BMA)) reveals interesting relations between initiator and surfactant hydrophilicity on the one hand and the hydrophilicity of the monomers on the other hand. For the water-soluble HEMA stable latexes are only obtained if hydrophobic initiators such as 2,2′-azobisisobutyronitrile or dibenzoyl peroxide in combination with alkyl sulfate surfactants with carbon chain lengths greater than 10 or surface active initiators of the 2,2′-azobis(N-2′-methylpropanoyl-2-amino-alkyl-1)-sulfonate type with alkyl chain lengths greater than 8 are employed. Stable nano size range poly(2-hydroxyethyl methacrylate) (PHEMA) particles have been prepared also by batch emulsion polymerization using ionic surface active initiators (inisurfs). The results clearly show that the formation of stable latex particles requires a proper choice of the initiator-emulsifier system regarding its hydrophilic-hydrophobic balance. The PHEMA particles prepared with surface-active initiators keep their identity and spherical shape even in the dried state whereas in the case of the other initiator-emulsifier systems complete coagulation and coalescence occurs during drying.     

Measuring the financial risks of New York dairy producers

The financial risks of a group of New York dairy producers were measured from 1988 through 1997 and were decomposed by source of risk by two procedures. Decomposition of the variance suggested major contributors to variability in returns to New York dairy farms were variabilities in purchased feed quantities and milk production; milk price variability contributed substantially less. Similarly, decomposing the Gini measure of income dispersion indicated that milk revenues and purchased feed expenditures contributed most to farm return inequality over time. Controlling feed costs and maintaining high and stable milk production appear to be the principal approaches that dairy producers can use to control their financial risks.     

The potential of runoff-farming in the Sahel region: Developing a methodology to identify suitable areas

Runoff-farming, a water harvesting technique, is the diversion of rain water from a collecting area to a cropping area, thereby increasing the quantity of water available for crop growth. This technique, applicable in various types, is regarded as necessary to secure and increase food production in semi-arid regions. Simultaneously it minimizes water erosion risk where it is applied. As the potential of runoff-farming has not been investigated, a methodology had to be developed to enable planners to identify suitable areas the most efficient way. Five main information sources are tapped: ground checks by various specialists, maps, data, aerial photographs and satellite images. The interpretation of the collected data yields in the quantification of the runoff water, the water requirements of the crops and the water storage capacity of the soil. All factors have to be validated and integrated into a decision model.     

Fate of the glucose degradation products 3-deoxyglucosone and glyoxal during peritoneal dialysis

Conventional fluids for peritoneal dialysis (PD) contain reactive glucose degradation products (GDPs) as a result of glucose breakdown during heat-sterilization. GDPs in PD fluids (PDFs) have been associated with the progressive alteration of the peritoneal membrane during long-term PD by cytotoxic effects and formation of advanced glycation endproducts (AGEs). In this study, we investigated the possible fate of two characteristic GDPs, 3-deoxyglucosone (3-DG) and glyoxal, during PD. In vivo, 3-DG and glyoxal concentrations, which were analyzed by high-performance liquid chromatography (HPLC), decreased in PDFs by 78% and 88% during 4 h of dwell time. The PDFs were then incubated in vitro in the presence of the most important reaction partners of GDPs in the peritoneal cavity. Neither human peritoneal mesothelial cells, human peritoneal fibroblasts, soluble protein, an insoluble collagen surface, nor components of spent dialysate led to a significant reduction of 3-DG or glyoxal after 6 h. Only after long-term incubation, a noticeable decrease of 3-DG was observed (-37% after three weeks), more likely due to spontaneous degradation reaction than formation of advanced glycation endproducts. These results suggest that in the course of PD, 3-DG, and glyoxal are absorbed into the organism and thus might contribute to the systemic pool of reactive carbonyl compounds.     

Aqueous heterophase polymerization of styrene—a study by means of multi-angle laser light scattering

An online multi-angle laser light scattering study of ab initio surfactant-free styrene emulsion polymerization reveals unexpected results regarding the development of the dispersity during the whole reaction starting from mixing styrene and water at reaction temperature. The experimentally observed change in the dispersity, which is an indirect measure of the average characteristic size of the colloidal objects, allows the identification of three characteristic intervals. During interval A the equilibration of styrene in water is characterized by the formation of styrene domains, which increase in number and size until an equilibrium state is reached. This means that there is virtually no homogeneous/molecular styrene in water solution but rather nanodroplets of about 200 nm in diameter (assuming spherical shape) are formed. During interval B, after initiation of the polymerization and particle formation, the dispersity increases again as the average size decreases and the number of scattering objects increases. The polymer particles suck up the monomer from the monomer nanodroplets, which leads to the disappearance of the nanodroplets and to a decrease in the average size. During interval C the average size increases again due to the predominantly growth of the polystyrene particles.     

The effect of recurrent episodes of clinical mastitis caused by gram-positive and gram-negative bacteria and other organisms on mortality and culling in Holstein dairy cows

The objective of this study was to estimate the effects of recurrent episodes of different types of clinical mastitis (CM) caused by gram-positive (Streptococcus spp., Staphylococcus aureus, Staphylococcus spp.) and gram-negative (Escherichia coli, Klebsiella, Citrobacter, Enterobacter, Pseudomonas) bacteria, and other organisms (Arcanobacterium pyogenes, Mycoplasma, Corynebacterium bovis, yeast, miscellaneous) on the probability of mortality and culling in Holstein dairy cows. Data from 30,233 lactations in cows of 7 dairy farms in New York State were analyzed. Cows were followed for the first 10 mo in lactation, or until death or culling occurred, or until the end of our study period. Generalized linear mixed models with a Poisson error distribution were used to study the effects of recurrent cases of the different types of CM and several other factors (herd, parity, month of lactation, current year and season, profitability, net replacement cost, other diseases) on cows’ probability of death (model 1) or being culled (model 2). Primiparous and multiparous cows were modeled separately because they had different risks of mortality and culling and potentially different CM effects on mortality and culling. Approximately 30% of multiparous cows had at least one case of CM in lactation compared with 16.6% of primiparous cows. Multipara also had higher lactational incidence risks of second (10.7%) and third (4.4%) cases than primipara (3.7% and 1.1%, respectively). For primipara, CM increased the probability of death, with each successive case occurring in a month being increasingly lethal. In multipara, gram-negative CM increased the probability of death, especially when the gram-negative case was the first or second CM case in lactation. Primiparous cows with CM were more likely to be culled after CM than if they did not have CM, particularly after a second or third case. In multipara, any type of CM increased the probability of being culled. Gram-negative CM cases were associated with the numerically highest risk of culling.     

Predicting success in college: A longitudinal study of achievement goals and ability measures as predictors of interest and performance from freshman year through graduation.

The authors examined the role of achievement goals, ability, and high school performance in predicting academic success over students' college careers. First, the authors examined which variables predicted students' interest and performance in an introductory psychology course taken their first semester in college. Then, the authors followed students until they graduated to examine continued interest in psychology and performance in subsequent classes. Achievement goals, ability measures, and prior high school performance each contributed unique variance in predicting initial and long-term outcomes, but these predictors were linked to different educational outcomes. Mastery goals predicted continued interest, whereas performance-approach goals predicted performance. Ability measures and prior high school performance predicted academic performance but not interest. The findings support a multiple goals perspective. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The role of achievement goals in the development of interest: Reciprocal relations between achievement goals, interest, and performance.

The dynamics of individual and situational interest and academic performance were examined in the college classroom and 7 semesters later in conjunction with achievement goals. At the beginning of an introductory psychology course, participants reported their initial interest in psychology, achievement goals, and situational interest in course lectures. At the end of the semester, participants (N = 858) reported their situational interest in course lectures and psychology. In the short term, relationships emerged among initial interest, achievement goals, situational interest, and class performance. Longitudinally, situational interest during the introductory course, independent of initial interest, predicted subsequent course choices. Results are discussed in terms of S. Hidi and K. A. Renninger's (2006) 4-phase model of interest development and the multiple goals model (J. M. Harackiewicz, K. E. Barron, P. R. Pintrich, A. J. Elliot, & T. M. Thrash, 2002). (PsycINFO Database Record (c) 2010 APA, all rights reserved)