Quantification of free ketene acetals and determination of cure kinetics of poly(ortho ester)s by a facile deuterium labeling method

A facile method was developed to quantify unreacted ketene acetals during polymerization of poly(ortho ester)s. The method was based on isotopic (deuterium) labeling of the unreacted ketene acetal groups arising from the diketene acetal monomer, 3,9-diethylidene-2,4,8,10-tetraoxaspiro[5,5]undecane (DETOSU). In deuterium oxide, free ketene acetals are hydrolyzed to an α-deuterated ester; ortho ester bonds are hydrolyzed to the nondeuterated analog. The relative abundance of the deuterated ester side chain can be quantified by gas chromatography-mass spectrometry (GC-MS). In the current method, aliquots of a diketene acetal/polyol(s) reaction mixture were dissolved (crosslinked polymers swollen) in methylene chloride and excess D₂O. The diketene acetal/polyol(s) reaction mixture was hydrolyzed under mildly acidic conditions to yield pentaerythritol dipropionate (PDP; hydrolysis product of DETOSU). PDP was extracted into an organic phase, silylated, and analyzed by GC-MS. Fragments corresponding to the C₂H₅C?O+ ion (57 a.m.u.) and C₂H₄DC?O+ ion (58 a. m. u.) were monitored and the quantity of free ketene acetal groups were calculated from the peak areas of the chromatograms. The precision of the method was ±0.1%. The accuracy, as compared to a parallel ¹H-NMR study, was within 5%. This method permits determination of the cure end-point of a poly(ortho ester) polymerization reaction to within ±0.25%. The curing kinetics agreed well with DSC branching/crosslinking measurements. © 1994 John Wiley & Sons, Inc.     

Effect of lipopolysaccharide on indices of peripheral and hepatic metabolism in lactating cows

Four multiparous lactating cows (175 to 220 d in milk [DIM]) were used in a 4 x 4 Latin square design to assess the effects of four doses (0.0, 0.5, 1.0, and 1.5 microg/kg of body weight) of lipopolysaccharide (LPS; Escherichia coli 0111:B4) on performance and plasma metabolite and hormone concentrations. In addition, effects of immune activation on in vitro hepatic metabolic capacity were evaluated in 12 multiparous lactating cows (150 to 220 DIM) infused with 0 (n = 6), 1.0 (n = 4) or 2.0 (n = 2) microg of LPS/kg. Milk production and DMI decreased linearly with LPS dose for 24 h after LPS infusion. Overall mean plasma tumor necrosis factor-alpha, insulin, glucagon, and cortisol concentrations increased linearly with LPS dose, and plasma beta-hydroxybutyrate decreased linearly by dose after LPS infusion. Infusion of LPS decreased the insulin:glucagon molar ratio, but did not affect plasma concentrations of growth hormone, insulin-like growth factor-1, leptin, or L-(+)-lactate. Plasma concentrations of glucose tended to increase initially and subsequently decrease, and there was a quadratic tendency for increased plasma nonesterified fatty acid concentrations after LPS administration. In vitro hepatic capacity for conversion of [1-(14)C]L-(+)-lactate and [1-(14)C]palmitate, but not [1-(14)C]propionate or [1-(14)C]L-alanine, to CO2 increased after LPS administration. Hepatic capacity to convert [1-(14)C]propionate to glucose tended to increase, but neither esterification nor the conversion of palmitate to acid soluble products was altered by LPS. The LPS infusion resulted in significant changes of endocrine mediators responsible for regulation of energy metabolism of lactating cows and tended to alter subsequent in vitro hepatic metabolic capacity.     

Mechanical properties of lettuce

The fracture properties of Spanish Iceberg and English Round lettuce tissues were investigated using a tensile test on notched specimens. The level of notch sensitivity was investigated for samples of differing colour and vein orientation. Vein orientation perpendicular to the test direction proved to be the most notch sensitive and samples with vein orientation parallel to the test direction proved to be very notch insensitive, samples with a diagonal (45°) orientation showed an intermediate response. This response was interpreted in terms of the interaction of veins with the crack path. The strengths of English Round tissues were broadly comparable with those of Spanish Iceberg although the upper limits depended on vein orientation and were in the order: parallel > diagonal perpendicular. A similar ranking of vein orientation was found in estimates of stiffness.     

The minimizing of blaming attributions and behaviors in delinquent families.

Parents' data were evaluated in three studies of families with a delinquent adolescent. Families were provided with different forms of a positive versus negative interactional (attributional) context. Study 1 demonstrated that the negative context elicited significantly more negative behaviors than did the positive context when parents interacted with each other and with their delinquent adolescent. Study 2 demonstrated that the dispositional attributions of parents were influenced by the manipulation of set, with a dissatisfied set producing negative blaming attributions and a satisfied set producing nonblaming, positive attributions. Study 3 demonstrated that parents' negative sets regarding their adolescent's negative behaviors, once established and discussed by the family for 5 min, were unresponsive to a subsequent positive reattribution regarding those behaviors. Taken together, the data provide some support for reattribution techniques such as relabeling. Yet, the data question the ease with which such techniques can be successful and challenge proponents of such techniques to develop methodologically sound empirical demonstrations of their effectiveness. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Suboptimality in human categorization and identification.

Categorization and identification decision processes were examined and compared in 4 separate experiments. In all tasks, the critical stimulus component was a line that varied across trials in length and orientation, and the optimal decision rules were always complex piecewise quadratic functions. Evidence was found that identification is mediated by separate explicit and implicit systems. In addition, a common type suboptimality was found in both categorization and identification. In particular, observers apparently approximated the piecewise quadratic functions of the optimal decision rules with simpler piecewise linear functions. A computational model, which was motivated by a recent neuropsychological theory of category learning, successfully accounted for this suboptimal performance in both categorization and identification. The model assigns a key role to the striatum and assumes the observed suboptimality was largely due to massive convergence of visual cortical cells onto single striatal units. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Deterioration of PCPV concrete

This paper presents results obtained from an experimental investigation into the deterioration of concretes used in prestressed concrete pressure vessels (PCPVs) in the UK. The experimental works were focused on the dependence of the residual properties of the thermally loaded concretes on the mix design (3 representative PCPVs), levels of exposed temperature (from 20 to 450°C), test age (3 months and 1 year) and exposure condition (sealed and unsealed). The residual properties investigated in this project were conducted by fully using both destructive (compressive, tensile splitting and static modulus) and non-destructive (dynamic modulus and ultrasonic pulse velocity) test techniques with the aim of better understanding and characterising the deterioration of PCPV concretes when subjected to both ambient and elevated temperatures under the environmental conditions likely to be experienced in real structures. Detailed statistical analyses and discussions on the experimental results were also performed and presented.     

An investigation of the grindability of two torrefied energy crops

The process of torrefaction alters the physical properties of biomass, reducing its fibrous tenacious nature. This could allow increased rates of co-milling and therefore co-firing in coal fired power stations, which in turn would enable a reduction in the amount of coal used and an increase in the use of sustainable fuels, without the need for additional plant. This paper presents an experimental investigation of the pulverisation behaviour of two torrefied energy crops, namely: willow and Miscanthus. A multifactorial method approach was adopted to investigate the three process parameters of temperature, residence time and particle size, producing fuels treated using four different torrefaction conditions. The untreated and torrefied fuels were subjected to standard fuel analysis techniques including ultimate analysis, proximate analysis and calorific value determination. The grindability of these fuels was then determined using a laboratory ball mill and by adapting the Hardgrove Grindability Index (HGI) test for hard coals. After grinding, two sets of results were obtained. Firstly a determination similar to the HGI test was made, measuring the proportion of sample passing through a 75 μm sieve and plotting this on a calibrated HGI chart determined using four standard reference coals of known HGI values. Secondly the particle size distributions of the entire ground sample were measured and compared with the four standard reference coals. The standard fuel tests revealed that temperature was the most significant parameter in terms of mass loss, changes in elemental composition and energy content increase. The first grindability test results found that the untreated fuels and fuels treated at low temperatures showed very poor grindability behaviour. However, more severe torrefaction conditions caused the fuels to exhibit similar pulverisation properties as coals with low HGI values. Miscanthus was found to have a higher HGI value than willow. On examining the particle size distributions it was found that the particle size distributions of torrefied Miscanthus differed significantly from the untreated biomass and had comparable profiles to those of the standard reference coals with which they had similar HGI values. However, only the torrefied willow produced at the most severe conditions investigated exhibited this behaviour, and the HGI of torrefied willow was not generally a reliable indicator of grindability performance for this energy crop. Overall it was concluded that torrefied biomass can be successfully pulverised and that torrefied Miscanthus was easier to grind than torrefied willow.     

Effect of calcium chloride on mechanical properties and microbiological characteristics of cv. Conservolea naturally black olives fermented at different sodium chloride levels

The effect of calcium chloride (CaCl₂)(5 gL^?1) and sodium chloride (NaCl) concentration (40, 60 and 8 gL^?1) on the microbiological and mechanical properties of naturally black olives of cv. Conservolea in brines was studied. In 40 and 60 g L^?1 brines the growth of lactic acid bacteria was favoured over that of yeasts, resulting in rather complete lactic acid fermentation as indicated by high free acidity (9.8–11.5 g lactic acid L^?1) and low pH (3.7–3.8). At 80 g L^?1 brine, yeasts were the dominant members of the microflora, rendering a product with lower acidity (8 g lactic acid L^?1) and higher pH (4.3–4.5). In the presence of CaCl₂ there was a consistent increase in the depth of the peripheral region in which cell wall breakage occurred. When cells separated, perforated walls were observed at sites associated with plasmodesmata. The flesh was strongest and stiffest when CaCl₂ was added to olives treated with 40 g L^?1 brine, consistent with cell wall breakage being the predominant mode of failure. The only observed effect on the mechanical properties of the skin was a stiffening at 60 g L^?1 brine on addition of CaCl₂. Copyright © 2007 Society of Chemical Industry