Insights into post-polymerisation modification of bio-based unsaturated itaconate and fumarate polyesters via aza-michael addition: Understanding the effects of C=C isomerisation.

Development of renewable bio-based unsaturated polyesters is undergoing a renaissance, typified by the use of itaconate and fumarate monomers. The electron-deficient C=C bond found on the corresponding polyesters allows convenient post-polymerisation modification to give a wide range of polymer properties; this is notably effective for the addition of nucleophilic pendants. However, preservation of unsaturated functionality is blighted by two undesirable side-reactions, branching/crosslinking and C=C isomerisation. Herein, a tentative kinetic study of diethylamine addition to model itaconate and fumarate diesters highlights the significance of undesirable C=C isomerisation. In particular, it shows that reversible isomerisation from itaconate to mesaconate (a poor Michael acceptor) is in direct competition with aza-Michael addition, where the amine Michael donor acts as an isomerisation catalyst. We postulate that undesired formation of mesaconate is responsible for the long reaction times previously reported for itaconate polyester post-polymerisation modification. This study illustrates the pressing need to overcome this issue of C=C isomerisation to enhance post-polymerisation modification of bio-based unsaturated polyesters. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1935-1945.

A beef herd model for simulating feed intake, animal performance, and manure excretion in farm systems.

A beef herd submodel was created for integration with other farm components to form a whole-farm model capable of simulating a wide range of beef production systems. This herd submodel determined the best available feed or feed mix to meet the fiber, energy, and protein requirements for each of up to six animal groups on the farm. The groups comprised any combination of cows, nursing calves, young heifers, yearling heifers, stockers, and finishing cattle. Protein, energy, and mineral requirements were determined for each group using the Cornell Net Carbohydrate and Protein System, Level 1. Diets were formulated to meet these requirements with available feeds, and the resulting feed intake, growth, and manure DM and nutrient (N, P, and K) excretions were predicted. Required feed characteristics included CP, ruminally degradable protein, acid detergent insoluble protein, NDF, P, and K concentrations. Feed intake was predicted by considering energy intake, potentially limited by fill, and exceeding a minimum roughage requirement. Fill and roughage limits were functions of feed NDF concentrations adjusted to consider particle size distribution and the relative rate of ruminal digestibility or the physical effectiveness of the fiber. The herd submodel was verified to predict feed intakes, nutrient requirements, diets, and manure excretions similar to those recommended or measured for beef animals. Incorporation of the beef herd submodel with other farm components, including crop growth (alfalfa, grass, corn, small grain, and soybean), harvest, storage, feeding, grazing, and manure handling, provided the Integrated Farm System Model. This comprehensive farm-simulation model is a useful research and teaching tool for evaluating and comparing the long-term performance, economics, and environmental impact of beef, dairy, and crop production systems.

The effects of grazing, liquid supplements, and implants on feedlot performance and carcass traits of Holstein steers.

In each of 2 yr, 20 Holstein steers (185+/-7 kg initial BW) were allocated to each of three treatments: pastured for 4.5 mo on grass/legume pastures and then fed 80% corn diets (DM basis) until slaughter; pastured for 4.5 mo on grass/legume pastures with ad libitum access to molasses-based protein supplements and fed 80% corn diets until slaughter; and placed in a feedlot and fed only 80% corn diets until slaughter (FEEDLOT). Half of the steers in each treatment were initially implanted with Revalor-S and not reimplanted. Supplemented steers on pasture had greater (P < 0.05) ADG than unsupplemented steers, and FEEDLOT steers gained faster and were fatter (P < 0.05) after 4.5 mo. Implanted steers had greater (P < 0.05) ADG with no significant treatment x implant status effect. Supplement intake was variable and related to ambient temperature. During the feedlot phase, steers previously on pasture had greater DMI and ADG (P < 0.05) but were not more efficient than FEEDLOT steers. Percentage of USDA Choice carcasses, fat thickness, dressing percentage, yield grade, and final weight were greater (P < 0.05) for FEEDLOT steers than for steers on other treatments. Implanting increased ADG of all steers but did not affect carcass traits, carcass composition, or feedlot performance during the finishing phase. Holstein steers consuming supplemented and unsupplemented pasture before slaughter will be leaner, have lower carcass weights, and have generally lower quality grades than those fed exclusively in a feedlot when slaughtered at similar ages.

Meat composition and palatability of Holstein and beef steers as influenced by forage type and protein source.

This experiment determined meat composition and palatability changes resulting from feeding Holstein (HOL) and crossbred beef (XB) steers diets containing corn silage (CS) or alfalfa haylage (AH) (forage type) and soybean meal (SM) or fish meal (FM) (protein source). Fifty-nine steers (30 HOL and 29 XB) were randomly assigned to diet combinations for a 2 x 2 x 2 (breed x forage x protein) factorial arrangement. Steers were fed to a fat-constant end point (fat depth over the longissimus muscle measured by ultrasound: 1.0 cm XB, .6 cm HOL). Proximate and fatty acid analysis and sensory evaluation were conducted on a rib eye roast and steaks, respectively, removed from the left side of each carcass at ribs 9 to 12. Proximate analysis of the longissimus muscle showed no significant difference (P greater than .05) in moisture, protein, or fat content due to breed, forage, or protein treatment. Forage type had no significant effect (P greater than .05) on amount of individual fatty acids found in longissimus muscle. However, total polyunsaturated fatty acids were higher (P greater than .05) for AH than for CS-fed animals. Longissimus muscle from steers fed FM had higher palmitoleic and lower stearic acid contents (both P less than .05) than longissimus muscle from animals fed SM. Muscle from HOL had higher palmitoleic and lower stearic acid contents than that from XB steers (both P less than .05). There was no significant interaction (P greater than .05) of breed with either diet treatment for individual fatty acid contents.(ABSTRACT TRUNCATED AT 250 WORDS)

Effects of forage and protein source on feedlot performance and carcass traits of Holstein and crossbred beef steers.

Fifty-eight Holstein and 58 crossbred beef steers were individually fed one of four isonitrogenous diets to evaluate the effects of forage source (corn silage and alfalfa haylage) and protein source (soybean meal and fish meal) on feedlot performance. Phase 1 diets (up to 354 kg of BW) were 40% forage and 60% concentrates and were fed for 70 to 136 d (depending on diet and breed group). Phase 2 diets (354 kg of BW until slaughter) were 20% forage and 80% concentrates and were fed for 127 to 150 d (depending on diet and breed group). Slaughter end points were .6 cm of 12th rib fat for Holsteins and 1.0 cm of rib fat for crossbreds using real-time ultrasonic estimates. The steers were fed for a maximum of 330 d each year. Forage source was a significant component of variation for most growth, efficiency, and carcass traits. Holstein and crossbred steers fed alfalfa haylage had significantly lower average daily gain, feed efficiency, dressing percentage, and empty body fat and required more days on feed to reach slaughter end points, but had higher total feed energy intake available for production. Steers fed corn silage diets had significantly greater energetic efficiency (P less than .05) than those fed alfalfa haylage, due to increased use of ME to produce fat in the carcass. Protein type did not influence gain, feed or energetic efficiency, energy intake, or most carcass traits. A significant protein system x forage source interaction among the four diets was detected for crossbred steers fed corn silage and fish meal, for which there was significantly greater feed conversion with lower energy intake above maintenance, possibly due to better fiber digestion and(or) amino acid flow to the lower tract. Alfalfa haylage plus soybean meal diets decreased (P less than .05) the percentage of Holsteins grading USDA Choice or higher. These results indicate that corn silage, because of greater energy concentration, was a more desirable forage in feedlot diets composed of less than or equal to 40% forage and that protein type (soybean meal and fish meal) in growing diets is not an important factor in feedlot performance or carcass traits of Holstein or crossbred steers that are fed these diets.

Evaluation of feed conversion in steers from a diallel of Simmental, Limousin, Polled Hereford, and Brahman beef cattle.

A total of 269 steers produced in a four-breed diallel mating design of Simmental, Limousin, Polled Hereford, and Brahman breeds were evaluated for the unadjusted and maintenance-adjusted total feed intake to total weight gain ratio. Time on feed ranged from 184 to 251 d. Covariate adjustments were made separately for age- and 12th rib fat-constant end points. Purebred, general combining ability, and maternal effects and heterosis were estimated. Effects of year, breed of dam, slaughter group, and days on feed accounted for most of the variation in feed conversion. Significantly higher unadjusted cumulative feed/gain ratios were found for steers from Brahman sires and for those from Simmental, Limousin, and Brahman dams. Adjustment to either fat- or age-constant values did not rerank breed groups, but a small reduction in the differences between these groups was detected for fat-constant efficiency. For maintenance-adjusted feed intake, progeny of Simmental and Limousin dams were less efficient than those of Polled Hereford and Brahman dams. Negative values for general combining ability, maternal effects, and heterosis would indicate less feed required per unit of weight gain. General combining ability for Polled Hereford crosses was negative and significant for cumulative feed/gain ratios, but no difference among dam breeds was found for the maintenance-adjusted ratio. Maternal effects for Limousin dams were positive and significant for all maintenance-adjusted ratios. Heterosis estimates for specific breed crosses were generally negative and ranged from -.87 to .22.

Evaluation of performance characteristics in a diallel among Simmental, Limousin, Polled Hereford and Brahman beef cattle. I. Growth, hip height and pelvic size.

Progeny of a diallel among Simmental, Limousin, Polled Hereford and Brahman breeds of cattle were evaluated over 5 yr for preweaning and postweaning growth, hip height and pelvic size. Calves from Brahman and Simmental dams had the highest preweaning gains and weaning weights, and those from Polled Hereford dams had the lowest (P less than .05). Differences in the availability of milk and postpartum compensatory gains in progeny of Brahman dams could have contributed to these results. However, calves from Simmental, Limousin and Polled Hereford dams had significantly greater feedlot daily gains than those from Brahman dams. Yearling hip height and pelvic area were lower for progeny of Polled Hereford dams, whereas calves from Simmental, Limousin and Brahman dams were not different for these traits. A series of linear comparisons among these four breeds using least-squares means to estimate general and specific combining ability and maternal effects found significant, negative maternal effects for Polled Hereford for preweaning gain and weaning weight. A positive maternal effect (P less than .05) for Limousin was found for feedlot gain. General combining ability and maternal estimates were significant and variable in most comparisons for yearling hip height and pelvic area. Heterosis estimates were positive and significant in all crosses with Brahman for preweaning gain, weaning weight, yearling weight, hip height and pelvic area. Significant, positive heterosis was also found in Polled Hereford crosses with Limousin and Simmental for preweaning gain, weaning weight and yearling weight.

Evaluation of performance characteristics in a diallel among Simmental, Limousin, Polled Hereford and Brahman beef cattle. II. Carcass traits.

Evaluations of steer and heifer progeny from a diallel mating design of Simmental, Limousin, Polled Hereford and Brahman beef cattle over 5 yr are presented. Traits evaluated included final weight, hot carcass weight, ribeye area, 12th rib fat thickness, marbling score, yield grade, dressing percentage and percentage of kidney, pelvic and heart fat. Progeny of Simmental sires were heavier at slaughter than those with Brahman sires (P less than .05), but no differences were found for carcass weight. Dressing percentage was higher for Limousin crosses compared with progeny of other sire breeds (P less than .05). Similar results were found for dam breeds, except that progeny of Limousin dams had heavier carcasses with a higher dressing percentage (P less than .05) than Brahman crosses. Crosses of Limousin and Simmental had larger ribeye areas (P less than .05) compared with calves of the other breeds. Progeny of Polled Hereford dams had higher marbling scores and were fatter than progeny of dams of other breeds (P less than .05). Heterosis estimates were significant for all Brahman crosses for final weight, carcass weight and ribeye area, but these contrasts were negligible for other traits. Estimates of general combining ability were positive and significant for Simmental for final weight, carcass weight, ribeye area and marbling score and were significant and negative for Limousin for final weight, fat thickness and yield grade. Maternal values were generally small.

Reproductive rates, birth weight, calving ease and 24-h calf survival in a four-breed diallel among Simmental, Limousin, Polled Hereford and Brahman beef cattle.

Calving and weaning rates, birth weight, calving ease, and 24-h calf survival were evaluated in a four-breed diallel of Simmental (S), Limousin (L), Polled Hereford (H) and Brahman (B) beef cattle in five calf crops. Limousin dams tended to have the highest calving and weaning rates because they were able to have heavier calves with less calving difficulty and higher survival rates. Brahman-sired calves were the heaviest at birth (P less than .05) and B dams produced the lightest calves (P less than .001). Lower birth weights tended to be the limiting factor on survival of these calves. A linear comparison among means to evaluate purebred, additive, maternal and specific combining ability effects showed most of the reduction in birth weight from B dams was due to maternal effects. Breed of dam accounted for a higher proportion of variation in calving ease than did sire breed. Simmental sires had significantly heavier calves at birth and S and H dams tended to have more calving difficulty and lower survival rates. Heterosis for these traits was generally not significant. Correlations were generally positive and significant for birth weight and calving ease, but were more variable for birth weight and survival. Linear regressions of calving ease on birth weight both within years and within dam-breed-year subclasses were very similar in that the association of these two traits was reduced as dam age increased.