Synthesis and Optoelectronic Properties of Nonpolar Polyrotaxane Insulated Molecular Wires with High Solubility in Organic Solvents

Hydrophilic polyanionic conjugated polyrotaxanes are readily synthesized in water by Suzuki coupling, but their high polarity and ionic nature limit the potential applications of these materials. Here, we demonstrate three methods for transforming these polar polyelectrolytes into nonpolar lipophilic insulated molecular wires. A water‐soluble polyfluorene‐alt‐biphenylene β‐cyclodextrin (CD) polyrotaxane was converted into nonpolar derivatives by methylation of the carboxylic acid groups with diazomethane and conversion of the hydroxyl groups of the CDs to benzyl ethers, trihexylsilyl ethers, benzoyl esters, and butanoate esters to yield polyrotaxanes that are soluble in organic solvents such as chloroform and cyclohexane. Elemental analysis, NMR spectroscopy, and gel permeation chromatography (GPC) data support the proposed structures of the organic‐soluble polyrotaxanes. The extents of reaction of the polyrotaxane CD hydroxyl groups were 55% for trihexylsilyl chloride/imidazole; 81% for benzyl chloride/sodium hydride; 72% for benzoyl chloride/pyridine/4‐dimethylaminopyridine; and 98% butanoic anhydride/pyridine/4‐dimethylaminopyridine. Alkylation, silylation, and esterification increase the bulk of the encapsulating sheath, preventing interstrand aggregation, increasing the photoluminescence efficiency in the solid state and simplifying the time‐resolved fluorescence decay. The organic‐soluble polyrotaxanes were processed into polymer light‐emitting diodes (PLEDs) from solution in nonpolar organic solvents, thereby excluding ionic impurities from the active layer.     

Effect of plant cultivation methods on content of major and trace elements in foodstuffs and retention in rats

BACKGROUND: Many consumers perceive organic foods as more nutritious than conventional foods. However, the existing evidence is insufficient to support or refute this belief. The purpose of the present study was to investigate the effect of three different model cultivation systems on selected major and trace element contents of dried foodstuffs (carrots, kale, peas, potatoes and apples) grown in two consecutive years, as well as mineral retention determined in 36 rats (second generation in a multi‐generation study) fed diets based on these foodstuffs from one year. RESULTS: Overall, there was no evident trend towards differences in element content of foodstuffs or diets due to the use of different cultivation systems, and differences between harvest years exceeded those seen between cultivation methods. Also, no significant differences in the retention of elements in rats fed diets derived from different cultivation systems were seen, since higher intake resulted in correspondingly higher excretion. CONCLUSION: This study does not support the belief that organically grown foodstuffs generally contain more major and trace elements than conventionally grown foodstuffs, nor does there appear to be an effect on the bioavailability of major and trace minerals in rats. Copyright © 2008 Society of Chemical Industry     

Antioxidative Effect of Seaweed Extracts in Chilled Storage of Minced Atlantic Mackerel (<Emphasis Type="Italic">Scomber scombrus</Emphasis>): Effect on Lipid and Protein Oxidation

In this study, antioxidant activity of absolute ethanol, 50 % ethanol and water extracts of two species of seaweeds namely, Fucus serratus and Polysiphonia fucoides were evaluated for their ability to retard lipid and protein oxidation in minced mackerel. Mackerel mince added with 0.5 g/kg of extracts was prepared. For comparison, BHT at 0.2 g/kg and a control with no added extracts were also prepared. The samples were stored at 5 °C for 8 days, and sampling was done at time 0, 1, 2, 4, 5 and 8 days. The 50 % ethanolic extracts of P. fucoides were found to be very effective in retarding lipid and protein oxidation, as it resulted in low levels of peroxide value, volatiles and carbonyl compounds and protected against the loss of α-tocopherol and tryptophan residues. In spite of the higher phenolic content, the absolute ethanol extracts of both species showed a pro-oxidative tendency in minced mackerel. Water extract with lowest phenolic content showed no antioxidant effect in minced mackerel. In conclusion, the 50 % ethanolic extracts of P. fucoides can be a potential source of natural antioxidants, as these extracts have antioxidant activities similar to synthetic antioxidants such as BHT. However, the extent of protection offered by these extracts against protein oxidation was not clear and further studies are needed to understand the nature of the interaction between proteins and these extracts.     

Quality of carrots as affected by pre‐ and postharvest factors and processing

The aim of this review is to provide an update on factors contributing to quality of carrots, with special focus on the role of pre‐ and postharvest factors and processing. The genetic factor shows the highest impact on quality variables in carrots, causing a 7–11‐fold difference between varieties in content of terpenes, β‐carotene, magnesium, iron and phenolics as well as a 1–4‐fold difference in falcarindiol, bitter taste and sweet taste. Climate‐related factors may cause a difference of up to 20‐fold for terpenes, 82% for total sugars and 30–40% for β‐carotene, sweet taste and bitter taste. Organic farming in comparison with conventional farming has shown 70% higher levels for magnesium and 10% for iron. Low nitrogen fertilisation level may cause up to 100% increase in terpene content, minor increase in dry matter (+4 to +6%) and magnesium (+8%) and reduction in β‐carotene content (?8 to ?11%). Retail storage at room temperature causes the highest reduction in β‐carotene (?70%) and ascorbic acid (?70%). Heat processing by boiling reduces shear force (?300 to ?1000%) and crispiness (?67%) as well as content of phenolics (?150%), terpenes (?85%) and total carotenes (?20%) and increases the risk of furan accumulation. Sensory and chemical quality parameters of carrots are determined mainly by genetic and climate‐related factors and to a minor extent by cultivation method. Retail temperature and storage atmosphere as well as heating procedure in processing have the highest impact in quality reduction. © 2013 Society of Chemical Industry     

Clinical trial of local anesthetic protocols for acute pain associated with caustic paste disbudding in dairy calves

Caustic paste disbudding is becoming more commonplace in North America. A large body of work has examined pain control for cautery disbudding and surgical dehorning, but fewer studies have evaluated pain control for caustic paste disbudding, and results conflict regarding benefits of local anesthesia. In humans, the pain associated with a caustic, chemical burn can differ in nature, duration, and intensity compared with a thermal burn. The objective of this clinical trial was to evaluate the effects of either a lidocaine cornual nerve block or a topical anesthetic incorporated into caustic paste on the acute pain of caustic paste disbudding. Seventy-two Holstein-Friesian calves housed in groups with an automated milk feeder were enrolled into 18 replicates balanced on age and assigned to 1 of 4 treatments: sham (S), placebo paste and a saline cornual block; topical (T), a novel caustic paste containing lidocaine and prilocaine, and a saline cornual block; cornual block (B), commercial caustic paste and a lidocaine cornual nerve block; and positive (P), commercial caustic paste and a saline cornual block. All calves received 0.5 mg/kg of meloxicam SC at the time of the block. Researchers were blinded to treatment group. Primary outcomes were validated pain behavior responses and pain sensitivity measured by algometry. Secondary outcomes consisted of respiratory and heart rate, latency to approach the evaluator, play behavior, feeding behavior, and standing and lying bout characteristics. Data were analyzed using linear, Poisson, and negative binomial regression models. Cornual-blocked calves had less pain sensitivity to 180 min after disbudding than all other groups; T and P calves had more pain sensitivity than S calves for the same time period. Compared with T and P calves, B and S calves had fewer pain behaviors until 120 min postdisbudding, decreased respiratory and heart rates, and a shorter latency to feed. The S calves exhibited more play behavior than other groups. Caustic paste appears to be acutely painful for at least 180 min, and this is reduced by a cornual nerve block but not by our novel paste. Because caustic paste may result in a different pain experience than cautery, use of a variety of metrics assessing affective state, physiologic responses, and normal behaviors, such as feeding and lying, should be included into future trials to help assess the welfare of calves disbudded by this method. We recommend that calves disbudded with caustic paste receive local anesthetic with a cornual nerve block as well as a nonsteroidal anti-inflammatory drug to mitigate acute pain.     

Smokeless tobacco topography and toxin exposure.

This study examined the relationship between oral smokeless tobacco (ST) topographical measures and biomarkers of tobacco and carcinogen exposure. During 2 weeks of baseline ad libitum ST use, 54 male participants (mean age=32.1+/-7.5 years) were required to record the time each dip was placed in and removed from their mouths. Urine samples were collected twice during baseline and analyzed for nicotine, cotinine, and their glucuronides (total nicotine and total cotinine) and for metabolites of the tobacco-specific carcinogen 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol and its glucuronides (total NNAL). The results suggest that frequency and duration measures of ST use (p<.01 to p<.001), particularly total dip duration, are significantly correlated with total cotinine, total nicotine, and total NNAL. These results suggest that how long a ST user has tobacco in his mouth is most predictive of tobacco toxin exposure.     

Inhibition of haemoglobin-mediated lipid oxidation in washed cod muscle and cod protein isolates by Fucus vesiculosus extract and fractions

The effects of Fucus vesiculosus extract and fractions towards haemoglobin- (Hb-) catalysed lipid oxidation in washed cod muscle system and cod protein isolates during ice storage were examined. The extract and fractions were characterised in terms of total phlorotannin content (TPC), 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity, ferrous ion-chelating ability and reducing power. Progression of oxidation was followed by determining rancid odour, thiobarbituric acid reactive substances (TBARS), redness and volatile oxidation compounds by gas chromatography (GC). In both washed cod muscle and protein isolates, phlorotannin-enriched ethyl acetate (EtOAc) fraction showed higher inhibitory effect than crude 80% ethanol (EtOH) extract. The addition of oligomeric phlorotannin-rich subfraction (LH-2) separated by Sephadex LH-20 chromatography, completely inhibited the initiation of lipid peroxidation in both systems throughout the entire study period (8 days). Its effectiveness at 300 mg/kg level was comparable to that of 100 mg/kg propyl gallate (PG), a highly effective synthetic antioxidant in muscle foods. Although polymeric phlorotannin-rich subfraction (LH-5) had similar level of TPC and chemical antioxidant activities as oligomeric subfraction LH-2, it was far less efficient in model systems. These results suggest that other factors rather than the intrinsic reactivity toward radicals could be responsible for the inhibitory effect of phlorotannins on lipid oxidation in fish muscle. This study highlights the great potential of oligomeric phlorotannins as novel natural antioxidants in fish and fish products.     

Alpha-tocopherol concentration and stereoisomer composition in plasma and milk from dairy cows fed natural or synthetic vitamin E around calving

The aim of this study was to compare the effects of supplementing dairy cows with 1000 IU/day of all-rac-alpha-tocopheryl acetate (SynAc), RRR-alpha-tocopheryl acetate (NatAc), or RRR-alpha-tocopherol (NatAlc), from approximately 3 weeks before estimated calving until 2 weeks after calving, on the concentration of alpha-tocopherol and its stereoisomers (RRR-, RSS-, RRS-, RSR- and the four 2S-forms of alpha-tocopherol) in blood and milk. An unsupplemented group was included as control. Blood samples were collected at 3, 2 and 1 weeks before estimated calving, at calving, and 3, 7 and 14 days after calving, while milk samples were taken twice within 24 h after calving and at 7 and 14 days in milk. Overall, time and treatment had significant effects on plasma alpha-tocopherol with higher concentrations in NatAc than in the other groups. In addition, SynAc had higher concentrations than Control, and NatAlc tended to be higher than Control. The lowest plasma concentrations were observed at calving and 3 days after calving. Independent of treatment, the concentration was higher in colostrum than in milk day 7 and 14 after calving. Analyses of the stereoisomer distribution in plasma and milk showed that, irrespective of dietary treatment, RRR-alpha-tocopherol was the most predominant form, constituting more than 86%, whereas the remaining part of alpha-tocopherol was made up by the three synthetic 2R isomers, while the 2S isomers only contributed less than 1% of the total alpha-tocopherol. In control cows and cows supplemented with natural vitamin E, the proportion of RRR-alpha-tocopherol in plasma and milk constituted more than 98% of the total alpha-tocopherol. In conclusion, the results indicate that daily oral supplementation of dairy cows with RRR-alpha-tocopheryl acetate gives the highest blood concentrations of alpha-tocopherol in the periparturient period. Analyses of the distribution of the individual stereoisomers of alpha-tocopherol further indicate that the bioavailability of RRR-alpha-tocopherol relative to synthetic stereoisomers in cattle is considerably higher than officially accepted until now.     

Wind characteristics in the North and Baltic Seas from the QuikSCAT satellite

The QuikSCAT mission provided valuable daily information on global ocean wind speed and direction from July 1999 until November 2009 for various applications including numerical weather prediction, ocean and atmospheric modelling. One new and important application for wind vector satellite data is offshore wind energy, where accurate and frequent measurements are required for siting and operating modern wind farms. The greatest advantage of satellite observations rests in their extended spatial coverage. This paper presents analyses of the 10 year data set from QuikSCAT, for the overview of the wind characteristics observed in the North and Baltic Seas, where most of Europe's offshore wind farms operate and more will be constructed. Significant issues in data availability are identified, directly related to the flagging schemes. In situ observations from three locations in the North Sea are used for comparisons. Mean biases (in situ minus satellite) are close to zero for wind speed and ‐2.7° for wind direction with a standard deviation of 1.2 m s ^{? 1} and 15°, respectively. The impact of using QuikSCAT and in situ measurements extrapolated to 10 m for wind power density estimations is assessed, accounting for possible influences of rain‐contaminated retrievals, the sample size, the atmospheric stability effects and either fitting the Weibull distribution or obtaining the estimates from the time series of wind speed observations.Copyright © 2012 John Wiley & Sons, Ltd.