Iron(II)‐based catalysts for ethene oligomerization

The synthesis of iron(II) complexes with various tridentate di(imino)pyridine ligands and their potential as ethene oligomerization catalysts are described. The ligands are characterized by ¹H‐ and ¹³C‐NMR spectroscopy and the complexes only by mass spectrometry due to their paramagnetism. After activation either with methylalumoxane (MAO) or with a heterogeneous cocatalyst consisting of partially hydrolyzed trimethylaluminum and silica gel, the prepared complexes proved to be good catalysts for the oligomerization of ethene. 1‐Octene, 1‐hexene, and 1‐decene were the major products, formed in very high isomeric purity (99.9 %). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 476–482, 2003     

Aqueous extract from the vegetative portion of Spanish black radish (Raphanus sativus L. var. niger) induces detoxification enzyme expression in HepG2 cells

The vegetative, or above ground, portion of radishes are not typically consumed and have not been characterized in terms of their phytochemical content or biological activity. The antioxidant capacity of the freeze-dried vegetative portion of mature Spanish black radishes (harvested 2 months after planting) was 3.7-, 3.6- and 2.9-fold greater than freeze-dried roots as assayed by ferric ion reducing antioxidant power (FRAP), total phenolics and oxygen radical absorbance capacity (ORAC), respectively. No carotenoids were detected in the roots, however the vegetative portion contained 905.0 and 421.2 μg/g of lutein and β-carotene, respectively. Despite differences in glucosinolate composition, a class of compounds related to the induction of detoxification enzymes, the aqueous extracts of roots and the vegetative portion similarly induced quinone reductase activity and the expression of multiple phase I and II detoxification enzymes in the HepG2 human hepatoma cell line. When juiced, the resulting freeze-dried juice and pulp of the vegetative portion maintained the ability to induce detoxification enzymes, although there were some differences in the phytochemical contents of these two dried materials. These data demonstrate that the ability of the vegetative portion of Spanish black radish, which has significantly greater antioxidant potential than roots, to induce detoxification enzyme expression was similar to that of the roots.     

Postprandial metabolism and endocrine status in veal calves fed at different frequencies

Veal calves fed by bucket often develop postprandial insulin resistance, hyperglycemia, and glucosuria during fattening. Automatic feeding systems allow feed intake for 24 h, and small ingested portions are expected to decrease postprandial glucose loads. We have studied metabolic and endocrine traits in calves that were either 1) fed identical daily amounts of whole milk plus milk replacer by a computer-programmed automatic feeder (> or =6 portions from 0800 to 2400 h) (GrA) or 2) fed by bucket at 0800 and 1630 h (GrB). Calves started at a body weight of 118 kg, and the experiment lasted for 3 wk. During wk 3, lactose was supplemented to stress postabsorptive glucose homeostasis. Feed intake and average daily gains in GrA and GrB were similar. Plasma concentrations during an 8-h period of glucose (in part), lactate, urea, and somatostatin (in wk 3), and of glucagon and insulin (wk 2 and 3) were smaller in GrA than in GrB, whereas growth hormone, insulin-like growth factor I, insulin-like growth factor binding protein-1 (wk 2), and prolactin concentrations (wk 2 and 3) were higher. Lactose supplementation in wk 3 enhanced transient postprandial hyperglycemia and hyperinsulinemia. Thus, there were marked metabolic and endocrine differences when calves sucked their feed in six or more portions during a 16-h period from an automatic feeder compared with twice daily drinking from a bucket. Ingestion of small portions by calves avoided marked hyperglycemia and lactate increments, and lower plasma urea concentrations mirrored enhanced nitrogen utilization, possibly mediated by the altered growth hormone, IGF-I and insulin status.     

Concentrate feeding strategy in lactating dairy cows: metabolic and endocrine changes with emphasis on leptin

This study aimed to evaluate metabolic and endocrine adaptations to energy intake in multiparous Holstein cows (n = 90; mean 9434 kg energy-corrected milk yield/305 d) over the first 20 wk postpartum and to assess the association of leptin with metabolic, endocrine, and zootechnical traits. Concentrates were fed automatically for 24 h at 30% (C30) or 50% (C50) of total dry matter intake (DMI) from wk 1 to 10 postpartum and at linearly reduced amounts thereafter. Roughage was fed for ad libitum intake. The DMI was measured over 24 h; milk yield and body weight (BW), twice/d; milk composition, 4 times/wk; and milk acetone, weekly. Blood samples for determination of metabolite, hormone, and electrolyte concentrations and enzyme activities were obtained at wk 2 prepartum, and at wk 1 to 16 and at wk 20 postpartum from 0730 to 0900. Body condition scores (BCS) and backfat thickness were measured postpartum and during wk 1, 4, 8, 12, 16, and 20. Energy balance (EB) was considerably lower, but milk yield only slightly lower, in C30 than C50. Metabolic stress was more marked in C30 than C50, expressed by lower, glucose, insulin, insulin-like growth factor-1 (IGF-1), triiodothyronine, milk protein, and lactose concentrations, higher nonesterified fatty acid, beta-hydroxybutyrate, growth hormone, and milk acetone concentrations, and an accelerated decrease in BCS and backfat thickness. Nevertheless, C30 adapted successfully and thus maintained high milk yields despite negative EB. Leptin concentrations were lower in C30 than in C50 over the first 20 wk postpartum and were positively associated with BCS, EB, BW, cholesterol, albumin, insulin, and IGF-1; negatively associated with DMI and triiodothyronine; and were higher in cows calving in spring than in fall. Leptin is one among several factors involved in the regulation of energy metabolism and may be important for overall homeostatic and homeorhetic control of metabolism and thus for maintenance of performance.     

Estimation of energy balance at the individual and herd level using blood and milk traits in high-yielding dairy cows

This study aimed to estimate individual and herd-level energy balance (EB) using blood and milk traits in 90 multiparous high-yielding Holstein cows, held on a research farm, from wk 1 to 10 postpartum (p.p.) and to investigate the precision of prediction with successively decreased data sets simulating smaller herd sizes and with pooled samples. Dry matter intake, milk yield, and BW were measured daily from parturition through wk 10 p.p. Milk composition was determined 4 times per week, and milk acetone was measured weekly. Blood samples for the determination of metabolites, hormones, electrolytes, and enzyme activities were taken weekly from wk 1 to 10 p.p. between 0730 and 0900. Body condition scores and ultrasonic measurements of backfat thickness and fat depth in the pelvic area were evaluated in wk 1, 4, and 8 p.p. Concentrations of glucose, cholesterol, urea, insulin, insulin-like growth factor-1, triiodothyronine, and thyroxine (T4) in blood plasma and of lactose and urea in milk were positively correlated with EB, whereas concentrations of nonesterified fatty acids (NEFA), creatinine, albumin, beta-hydroxybutyrate, and growth hormone and enzyme activities in blood, and concentrations of fat, protein, fat:lactose ratio, and acetone in milk were negatively correlated with EB. Leptin concentration was not correlated to EB over the first 10 wk p.p. To estimate EB linear mixed-effects, models were developed by backward selection procedures. The most informative traits for estimation of EB were the fat:lactose ratio in milk and NEFA and T4 concentrations in blood. The precision of estimation of EB in individual cows was low. Using blood in addition to milk traits did not result in higher precision of estimation of herd-level EB, and decreasing sample sizes considerably lowered the precision of EB prediction. Estimation of overall mean herd-level EB over the first 10 wk p.p. using pooled samples was precise even with small sample sizes, but does not consider the level of EB in particular weeks. In conclusion, estimation of herd-level EB at individual weeks using milk traits only has practical implication with herd sizes of > or = 100 cows if calving is highly seasonal and of or = 400 cows if calving is uniformly distributed. Using blood in addition to milk traits does not improve precision of estimation of herd-level EB, regardless of sample size.     

Prolonged colostrum feeding enhances xylose absorption in neonatal calves

Colostrum contains numerous components that influence gastrointestinal development in neonates. To test the influence of differences in duration of colostrum feeding in newborn calves on gastrointestinal absorptive capacity, .5 g xylose/kg BW was administered on d 5 of life. Calves of group GrC6 were fed colostrum from the first six milkings on the first 3 d and then milk replacer. Calves of group GrC1 were fed first colostrum only and then milk replacer in the same amounts as calves of group GrC6. Calves of group GrM were fed only milk replacer: they received no colostrum. The rise of plasma xylose after xylose intake was greater (P < .05) in GrC6 and GrC1 than in GrM but not significantly greater in GrC6 than in GrC1. Basal and mean plasma glucose concentrations on d 5 of life were higher in GrC6 than in GrM, but there was no difference in the magnitude of its postprandial rise. The data indicate greater xylose absorptive capacity in calves after prolonged colostrum intake compared with calves fed only milk replacer.     

Lung cancer mortality in a French cohort of hard-metal workers

A cohort mortality study was carried out among workers of a plant producing hard metals using cobalt as a binder. This study was aimed at assessing possible lung cancer risks in relation with cobalt exposure. Seven hundred nine male workers with at least 1 year of employment were included in the cohort and followed for mortality from 1956 to 1989. Job histories were provided by the administration of the plant, whereas smoking habits were collected from medical records and by interview. The causes of deaths were ascertained from hospital and general practitioner records. The observed numbers of deaths (obs) were compared with the expected based on national rates with adjustment for age, sex, and calendar time (standardized mortality ratio; SMR). The overall mortality did not differ from that expected (obs = 75, SMR = 1.05), whereas mortality due to lung cancer was in significant excess (obs = 10, SMR = 2.13). This excess was higher among workers employed in the areas with the highest exposure (obs = 6, SMR = 5.03). No trend was observed, however, with duration of employment or time since first employment. Smoking data were available for 81% of the workers and 69% of the deceased and showed that smoking alone does not account for these lung cancer excesses, yet, because of the small numbers involved, no firm conclusion should be drawn from this study.     

Phosphoproteomic Analysis of Subcutaneous and Omental Adipose Tissue Reveals Increased Lipid Turnover in Dairy Cows Supplemented with Conjugated Linoleic Acid

Phosphoproteomics is a cutting-edge technique that can be utilized to explore adipose tissue (AT) metabolism by quantifying the repertoire of phospho-peptides (PP) in AT. Dairy cows were supplemented with conjugated linoleic acid (CLA, n = 5) or a control diet (CON, n = 5) from 63 d prepartum to 63 d postpartum; cows were slaughtered at 63 d postpartum and AT was collected. We performed a quantitative phosphoproteomics analysis of subcutaneous (SC) and omental (OM) AT using nanoUPLC-MS/MS and examined the effects of CLA supplementation on the change in the phosphoproteome. A total of 5919 PP were detected in AT, and the abundance of 854 (14.4%) were differential between CON and CLA AT (p ≤ 0.05 and fold change ± 1.5). The abundance of 470 PP (7.9%) differed between OM and SC AT, and the interaction treatment vs. AT depot was significant for 205 PP (3.5% of total PP). The integrated phosphoproteome demonstrated the up- and downregulation of PP from proteins related to lipolysis and lipogenesis, and phosphorylation events in multiple pathways, including the regulation of lipolysis in adipocytes, mTOR signaling, insulin signaling, AMPK signaling, and glycolysis. The differential regulation of phosphosite on a serine residue (S777) of fatty acid synthase (FASN) in AT of CLA-supplemented cows was related to lipogenesis and with more phosphorylation sites compared to acetyl-coenzyme A synthetase (ACSS2). Increased protein phosphorylation was seen in acetyl-CoA carboxylase 1 (ACACA;8 PP), FASN (9 PP), hormone sensitive lipase (LIPE;6 PP), perilipin (PLIN;3 PP), and diacylglycerol lipase alpha (DAGLA;1 PP) in CLA vs. CON AT. The relative gene expression in the SC and OM AT revealed an increase in LIPE and FASN in CLA compared to CON AT. In addition, the expression of DAGLA, which is a lipid metabolism enzyme related to the endocannabinoid system, was 1.6-fold higher in CLA vs. CON AT, and the expression of the cannabinoid receptor CNR1 was reduced in CLA vs. CON AT. Immunoblots of SC and OM AT showed an increased abundance of FASN and a lower abundance of CB1 in CLA vs. CON. This study presents a complete map of the SC and the OM AT phosphoproteome in dairy cows following CLA supplementation and discloses many unknown phosphorylation sites, suggestive of increased lipid turnover in AT, for further functional investigation.     

Effect of pre- and postpartum supplementation with lipid-encapsulated conjugated linoleic acid on reproductive performance and the growth hormone–insulin-like growth factor-I axis in multiparous high-producing dairy cows

The objective of the study was to evaluate the effect of prepartum and postpartum (PP) supplementation with 2 isomers of conjugated linoleic acid (CLA) on reproductive parameters and some related metabolic factors in dairy cows. High-producing, multiparous Holstein Friesian cows (n = 60) were allotted to 3 treatment groups: the CLA1 group (n = 20) was supplemented with 70 g of lipid-encapsulated CLA providing 7 g each of cis-9,trans-11 and trans-10,cis-12 CLA from d 21 (d 21) before expected calving until d 7 after artificial insemination (AI), that is, until 77 to 91 d PP; the CLA2 group (n = 20) was supplemented with the same amount of CLA beginning at calving until d 7 after AI; and the control group (n = 20) received an isocaloric, isonitrogenous, and isolipidic diet. Blood samples were taken weekly to measure glucose, insulin, insulin-like growth factor-I (IGF-I), and leptin. Liver biopsy was performed in 10 cows per group for growth hormone receptor 1A and IGF-I mRNA analyses. At d 49 to 63 PP, ovulation was synchronized with the Pre-Synch protocol followed by fixed-time AI. Milk progesterone was monitored from calving until d 35 post-AI. Cows returning to estrus following AI were inseminated. Supplementation with CLA before calving improved the recovery of plasma leptin levels in the early PP period (from the day of calving until wk 3 PP; treatment effect). Later PP (wk 5), plasma IGF-I, and leptin remained significantly higher in both CLA1 and CLA2 groups compared with control, although hepatocellular IGF-I mRNA was not different among groups. Plasma IGF-I levels remained higher in both CLA-treated groups on the day of AI. Growth hormone receptor 1A mRNA levels in hepatic tissue decreased in all groups, reaching a nadir in the first week PP. Days to first PP ovulation did not differ between groups; however, both supplemented groups conceived earlier compared with control (d 97 ± 19, d 97 ± 23, and d 113 ± 30 for CLA1, CLA2, and control, respectively). Plasma progesterone concentration was higher in both supplemented groups on d 2 to 5 following the synchronized ovulation than in controls. We concluded that CLA supplementation around calving alters PP metabolic signals as reflected by higher plasma leptin and IGF-I levels. Conjugated linoleic acid stimulated early luteal function and reduced the PP interval to conception.