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.

Two separate outflows in the dual supermassive black hole system NGC 6240.

Theoretical models and numerical simulations have established a framework of galaxy evolution in which galaxies merge and create dual supermassive black holes (with separations of one to ten kiloparsecs), which eventually sink into the centre of the merger remnant, emit gravitational waves and coalesce. The merger also triggers star formation and supermassive black hole growth, and gas outflows regulate the stellar content1-3. Although this theoretical picture is supported by recent observations of starburst-driven and supermassive black hole-driven outflows4-6, it remains unclear how these outflows interact with the interstellar medium. Furthermore, the relative contributions of star formation and black hole activity to galactic feedback remain unknown7-9. Here we report observations of dual outflows in the central region of the prototypical merger NGC 6240. We find a black-hole-driven outflow of [O III] to the northeast and a starburst-driven outflow of Hα to the northwest. The orientations and positions of the outflows allow us to isolate them spatially and study their properties independently. We estimate mass outflow rates of 10 and 75 solar masses per year for the Hα bubble and the [O III] cone, respectively. Their combined mass outflow is comparable to the star formation rate 10 , suggesting that negative feedback on star formation is occurring.

High molecular gas fractions in normal massive star-forming galaxies in the young Universe.

Stars form from cold molecular interstellar gas. As this is relatively rare in the local Universe, galaxies like the Milky Way form only a few new stars per year. Typical massive galaxies in the distant Universe formed stars an order of magnitude more rapidly. Unless star formation was significantly more efficient, this difference suggests that young galaxies were much more molecular-gas rich. Molecular gas observations in the distant Universe have so far largely been restricted to very luminous, rare objects, including mergers and quasars, and accordingly we do not yet have a clear idea about the gas content of more normal (albeit massive) galaxies. Here we report the results of a survey of molecular gas in samples of typical massive-star-forming galaxies at mean redshifts of about 1.2 and 2.3, when the Universe was respectively 40% and 24% of its current age. Our measurements reveal that distant star forming galaxies were indeed gas rich, and that the star formation efficiency is not strongly dependent on cosmic epoch. The average fraction of cold gas relative to total galaxy baryonic mass at z = 2.3 and z = 1.2 is respectively about 44% and 34%, three to ten times higher than in today's massive spiral galaxies. The slow decrease between z approximately 2 and z approximately 1 probably requires a mechanism of semi-continuous replenishment of fresh gas to the young galaxies.

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.

The dynamics of concussive head impacts in rugby and Australian rules football.

A study was commenced in 1998 at the University of New South Wales (UNSW) to investigate the dynamics of head impacts in football which resulted in concussion. Sixty-eight cases of medically verified concussion from Australian Rules Football and 32 from Rugby Union and Rugby League were analyzed. Video of each injury event was analyzed to obtain descriptive data regarding the head impact site and striking object. The video was analyzed quantitatively to obtain estimates of the closing speeds. A secondary analysis was undertaken using the conservation of momentum and energy relationships to estimate the change in velocity of the head during the impact, the change in momentum of the head, and the energy imparted to the head. Ninety-seven cases involved direct head contact, whereas three cases involved impulsive loading via the trunk. The majority of impacts were to the tempero-parietal region, and the striking body segment was commonly the arm or shoulder/thorax. The mean change in velocity of the head and head impact energy for all 97 cases of direct head impact were 4 m x s(-1) and 56 J, respectively. Head impact energy can be used as a performance criteria for testing and developing headgear for rugby and Australian rules football.

Antenatal care. Which tests and when.

A variety of tests form an important component of antenatal care. They are performed in association with clinical assessments to evaluate the health of the mother and fetus during pregnancy. This article reviews the tests that are available and those performed routinely during the antenatal care of a patient. Tests commonly used to monitor the various problems and complications that occur in pregnancy are also described. Appropriate interpretation of the results, to ensure a satisfactory outcome at the end of the 9 months gestation, is discussed.

Effects of CoA and acyl-CoA on Ca(2+)-permeability of endoplasmic-reticulum membranes from rat liver.

We have studied the effects of CoA and palmitoyl-CoA on Ca2+ movements and GTP-dependent vesicle fusion in rat liver microsomes. (1) Inhibition of membrane fusion by CoA depends on esterification of CoA to long-chain acyl-CoA using endogenous non-esterified fatty acids. (2) Binding of long-chain acyl-CoA to microsomal membranes is inhibited by BSA, which also relieves inhibition of membrane fusion. (3) Under conditions where acyl-CoA binding is inhibited, CoA causes increased Ca2+ accumulation, apparently by decreasing the Ca2+ leak rate. (4) Conversely, palmitoyl-CoA, in the presence of BSA, causes Ca2+ efflux. (5) The decrease in Ca(2+)-permeability caused by CoA does not depend on the presence of ATP or GTP, and is irreversible in the short term. (6) Using 14C-labelled CoA we show that CoA derivatives can be formed from endogenous components of microsomal membranes in the absence of ATP. (7) The results are interpreted in terms of a Ca(2+)-permeability which is controlled by CoA and/or long-chain acyl-CoA esters.

Comparison of PCR with southern hybridization for the routine detection of immunoglobulin heavy chain gene rearrangements.

The development of a reliable polymerase chain reaction (PCR) technique for the routine detection of clonal immunoglobulin heavy chain (IgH) gene rearrangements would represent an attractive alternative to Southern hybridization analysis because of the relative simplicity of PCR protocols, and because the requirements for both quality and quantity of DNA would be considerably less stringent. To assess the utility of PCR for the routine detection of clonal IgH gene rearrangements, samples from 123 adult patients were evaluated and analysis by PCR amplification using IgH Framework 1 or Framework 3 variable region consensus primers was compared with analysis by restriction endonuclease digestion and Southern hybridization with genomic, IgH probes. The authors found that 90% of IgH genes found to be rearranged by Southern hybridization are detected by the PCR technique. An additional 9 patient samples had clonal IgH gene rearrangements that were detectable by PCR alone. Eight of these nine patients had a history of a clonal hematopoietic process at either the morphologic or molecular level, and six had a history of a B-cell malignancy. It is likely that these specimens contained clonal lymphoid populations undetected by the Southern hybridization technique. Thus, the diagnostic sensitivity and specificity of the PCR method for the detection of B-cell tumors were 91% and 95%, respectively. The combination of improved analytical sensitivity and specimen flexibility of the IgH PCR assay could make it the method of choice for the routine detection of clonal IgH gene rearrangements, if minor improvements in the diagnostic sensitivity of the assay can be achieved.

Optimization for detection of cytomegalovirus by the polymerase chain reaction (PCR) in clinical samples.

PCR is 100 times more sensitive than traditional tube culture for detecting cytomegalovirus (CMV) but may require up to 12 reactions per specimen (Sandin et al., 1991). In order to make the assay practical for use in a clinical laboratory the procedure used to detect CMV must be simplified. In this study, the effect of reducing the number of reactions per specimen on sensitivity and specificity of the PCR assay was evaluated. 53 residual samples from specimens processed for CMV by shell vial assay/routine tube tissue culture (SVA/TTC) were analyzed by PCR. The residual samples were separated into a supernatant and pellet fractions, then tested for CMV with primers to the immediate early (IEP) and late protein (LP) genes using a nested procedure. To exclude false negatives due to the presence of inhibitors in the sample fractions, all fractions were tested for the presence of the human myosin heavy chain gene also using a nested procedure. SVA/TTC had a sensitivity and specificity of 52/96% in comparison to PCR when data from all 12 PCR reactions was considered. However, high sensitivity and specificity were retained when only the data of the IEP primers with two samples were considered. The results from examining only the 1:10 dilution of pellet and the undiluted supernatant by PCR provided a 60% increase in sensitivity over SVA/TTC, high specificity and a clinically feasible assay.

Effects of CoA and acyl-CoAs on GTP-dependent Ca2+ release and vesicle fusion in rat liver microsomal vesicles.

(1) CoA (IC50 23 microM) and acyl-CoAs (IC50 values 15-18 microM) inhibit GTP-dependent vesicle fusion in rat liver microsomal vesicles. Acyl-CoAs of carbon chain length C8 and C20 are much less effective than acyl-CoAs of carbon chain length C14-C18. The effect of CoA is mimicked by dephospho-CoA, but not by desulpho-CoA. High acyl-CoA concentrations (50 microM) appear to favour formation of small vesicles (budding), while 50 microM CoA does not. (2) Low concentrations of CoA (EC50 2 microM) and palmitoyl-CoA (10 microM) cause re-accumulation of Ca2+ released in response to GTP. This re-accumulation is into an Ins(1,4,5)P3-sensitive compartment. By investigation of the effects of CoA and palmitoyl-CoA on the thapsigargin-induced passive leak rate of Ca2+, and on the latency of the mannose-6-phosphatase of the vesicles, we conclude that CoA and palmitoyl-CoA cause decreased vesicle permeability rather than stimulation of Ca2+ pumping activity. (3) It is suggested that GTP-induced membrane fusion in rat liver microsomes involves an as yet uncharacterized acylation-deacylation reaction which is required to produce complete vesicle sealing.

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.

Fluoroaluminate treatment of rat liver microsomes inhibits GTP-dependent vesicle fusion.

1. Inhibition of GTP-dependent membrane fusion of rat liver microsomes requires preincubation of the membranes with GDP (17 microM) and relatively high Mg2+ concentration (0.5 mM) as well as AlCl3 (30 microM) and KF (5 mM). Preincubation is required for maximal inhibition (75%). 2. Vesicle fusion in rat liver microsomes has been demonstrated in the absence of polyethylene glycol (PEG). Further, inhibition by AlF4- of GTP-dependent vesicle fusion in the absence of PEG has been demonstrated. 3. Under similar preincubation conditions AlF4- can bring about inhibition (80%) of the high-affinity PEG-stimulated GTPase activity in rat liver microsomes, previously described by Nicchitta, Joseph & Williamson [(1986) FEBS Lett. 209, 243-248]. 4. Preincubation of small-Mr GTP-binding proteins (Gn proteins) on nitrocellulose strips with GDP (20 pM), AlCl3 (30 microM) and KF (5 mM) results in inhibition of binding of guanosine 5'-[gamma-[35S]thio]triphosphate to Gn proteins. The extent of inhibition of this binding differs for different Gn proteins.

Anomalous kinetic visual fields found in family members of patients with a confirmed diagnosis of Gilles de la Tourette syndrome.

Three visual manifestations of Gilles de la Tourette syndrome (TS), a neuropsychiatric disorder, have been previously reported. In this paper we report anomalies in the measured kinetic paracentral visual field of TS patients and their family members. We found that 96% of TS patients exhibited paracentral kinetic visual field defects (nasal and temporal steps, enlargement, "ringing," and/or baring of the blind spot). Ninety-three percent of fathers of TS children and, surprisingly, about 80% of mothers exhibit these characteristic visual field anomalies. Sample data and examples of family studies are reported.