Effect of self-complementary motifs on phase compatibility and material properties in blends of supramolecular polymers

Applicability of supramolecular polymers blending in preparation of materials with tunable properties is reported. The effect of strongly dimerising 2-ureido-4[1H]-pyrimidinone (UPy) end groups on phase compatibility in binary polymer blends was studied. A low molecular weight poly(tetrahydrofuran) diol was functionalized with UPy moieties (PTHF(UPy)₂, a soft material) and mixed with varying amounts of low molecular weight UPy functionalized polycaprolactone di- and triol (PCL(UPy)₂ and PCL(UPy)₃, both relatively strong and stiff materials). Thermal studies showed that T_g of the homopolymers shifted to intermediate temperatures. AFM observation suggested that the phase domain decreased significantly after UPy functionalization of diols. Also the mechanical properties improved at a higher rate than those predicted by the rule of mixtures. These findings indicate that blend components are placed in intimate contact as a result of the UPy-UPy interactions. The reversible crosslinking by PCL(UPy)₃ gave better control still over the mechanical properties of the supramolecular polymer blends.     

Characterization of melt flow instabilities in polyethylene/carbon nanotube composites

The effect of single (SWCNT) and multi- (MWCNT) walled carbon nanotubes on the melt flow instabilities of polyethylenes with different topologies was characterized by means of a novel capillary rheometer allowing in-situ measurements of the pressure fluctuations inside the die and by scanning electron microscopy (SEM) analysis. Our results show that carbon nanotubes modify the main characteristics of the spurt instability developed by the linear polyethylene. Furthermore, the sharkskin instability, developed in short chain branched polyethylene, is reduced at low amounts of MWCNT and SWCNT. Noteworthy, the critical shear rate for the on-set of the spurt and the sharkskin instabilities decreases in the nanocomposites due to the physical interactions between the polymer and the nanofiller.At high shear rates, the gross melt fracture instability is completely erased in the nanocomposites based on the linear polymer whereas in short chain branched polyethylene the amplitude of this bulk distortion is rather moderated. These changes were confirmed by on-line pressure measurements using the novel capillary rheometer set-up. Based on our results, it is concluded that carbon nanotubes drastically affect the non-linear molecular dynamic leading to polyethylene melt flow instabilities.     

Fabrication of Sub‐10 nm Metallic Lines of Low Line‐Width Roughness by Hydrogen Reduction of Patterned Metal–Organic Materials

The fabrication of very narrow metal lines by the lift‐off technique, especially below sub‐10 nm, is challenging due to thinner resist requirements in order to achieve the lithographic resolution. At such small length scales, when the grain size becomes comparable with the line‐width, the built‐in stress in the metal film can cause a break to occur at a grain boundary. Moreover, the line‐width roughness (LWR) from the patterned resist can result in deposited metal lines with a very high LWR, leading to an adverse change in device characteristics. Here a new approach that is not based on the lift‐off technique but rather on low temperature hydrogen reduction of electron‐beam patterned metal naphthenates is demonstrated. This not only enables the fabrication of sub‐10 nm metal lines of good integrity, but also of low LWR, below the limit of 3.2 nm discussed in the International Technology Roadmap for Semiconductors. Using this method, sub‐10 nm nickel wires are obtained by reducing patterned nickel naphthenate lines in a hydrogen‐rich atmosphere at 500 °C for 1 h. The LWR (i.e., 3 σ_LWR) of these nickel nanolines was found to be 2.9 nm. The technique is general and is likely to be suitable for fabrication of nanostructures of most commonly used metals (and their alloys), such as iron, cobalt, nickel, copper, tungsten, molybdenum, and so on, from their respective metal–organic compounds.     

Probing enzyme promiscuity of SGNH hydrolases

Several hydrolases of the SGNH superfamily, including the lipase SrLip from Streptomyces rimosus (Q93MW7), the acyl-CoA thioesterase I TesA from Pseudomonas aeruginosa (Q9HZY8) and the two lipolytic enzymes EstA (from P. aeruginosa, O33407) and EstP (from Pseudomonas putida, Q88QS0), were examined for promiscuity. These enzymes were tested against four chemically different classes of a total of 34 substrates known to be hydrolysed by esterases, thioesterases, lipases, phospholipases, Tweenases and proteases. Furthermore, they were also analysed with respect to their amino acid sequences and structural homology, and their phylogenetic relationship was determined. The Pseudomonas esterases EstA and EstP each have an N-terminal domain with catalytic activity together with a C-terminal autotransporter domain, and so the hybrid enzymes EstA(N)-EstP(C) and EstP(N)-EstA(C) were constructed by swapping the corresponding N- and C-terminal domains, and their hydrolytic activities were compared. Interestingly, substrate specificity and kinetic measurements indicated a significant influence of the autotransporter domains on the catalytic activities of these enzymes in solution. TesA, EstA and EstP were shown to function as esterases with different affinities and catalytic efficacies towards p-nitrophenyl butyrate. Of all the enzymes tested, only SrLip revealed lipase, phospholipase, esterase, thioesterase and Tweenase activities.     

Italian ryegrass silage in winter feeding of organic dairy cows: forage intake, milk yield and composition

BACKGROUND: Organic milk production aims at efficient use of home‐grown feeds, especially forages, to minimise the quantity of purchased feeds. In conventional agriculture, Italian ryegrass (Lolium multiflorum Lam.) is known for its high energy content and palatability, and the aim of the present study was to examine its suitability as feed for organic dairy cows. Therefore a feeding trial was conducted comparing a diet including 50% (of silage dry matter (DM)) of Italian ryegrass silage with a control diet based on grass/clover silage (a mixture of the second cut from permanent grassland and the second cut from a perennial clovergrass ley) alone. RESULTS: Inclusion of Italian ryegrass silage in the diet increased forage intake significantly (14.5 vs 13.4 kg DM in the control group) and concentrate intake did not differ, but milk yield was slightly lower (20.3 vs 21.0 kg) owing to the low energy and protein concentration of Italian ryegrass silage. CONCLUSION: Italian ryegrass was indeed found to be highly palatable, confirming in principle its suitability as feed for organic dairy cows. However, higher energy and protein concentrations in this forage would be necessary to translate the high intakes of Italian ryegrass silage into improved milk production as well. Copyright © 2010 Society of Chemical Industry     

Functional properties of Lactobacillus strains isolated from kimchi

The objective of this study was to evaluate the functional properties of lactic acid bacteria (LAB) from kimchi, a traditional Korean fermented vegetable product generally consumed raw as a side-dish with practically every meal.Twelve mild acid producing facultatively heterofermentative Lactobacillus strains were selected for their potential as starter cultures for fermentation of kimchi, and evaluated for their functional properties. Eleven strains were identified as Lactobacillus sakei and one as Lactobacillus plantarum. The strains identified as L. sakei differed in some physiological features; of particular interest was the fact that 9 of these strains produced L(+) lactic acid from glucose in presence of acetate.All strains were able to survive gastrointestinal conditions simulating stomach and duodenum passage. In addition, they showed higher adherence to HT-29 cells than Lactobacillus rhamnosus GG, a commercial probiotic strain used worldwide. These strains also showed antimicrobial activity against a number of food-borne pathogens. Their ability to lower cholesterol was demonstrated by BSH (bile salt hydrolytic) activity, and cholesterol assimilation tests in vitro. The results suggest the probiotic potential of these strains for use in kimchi fermentation.     

Concentration and distribution of heavy metals in urban airborne particulate matter in Frankfurt am Main, Germany

Heavy metal concentrations were measured in airborne dust collected at three sites with different traffic densities from August 2001 to July 2002 in the Frankfurt am Main area. Bulk samples of particulate matter (PM) with an aerodynamic equivalent diameter of <22 microm were collected on cellulose nitrate filters using air filtration devices. Fractionated samples of PM with an aerodynamic equivalent diameter of <10 microm were collected using an eight-stage Andersen impactor. Pb, Cd, Mn, Ni, Zn, V, As, Sb, Cu, Cr, Co, and Ce were determined by inductively coupled plasma sector field mass spectrometry, Pt and Rh were determined by adsorptive voltammetry, and Pd was determined by total reflection X-ray fluorescence analysis. The results show that the highest airborne heavy metal concentrations occurred at the main street with a large volume of traffic. With the exception of Co, V, Ce, and Mn, the heavy metals had an elevated enrichment factor compared to their concentrations in the continental crust. The main street site was especially contaminated with Sb, Zn, Cu, V, and Ni. Motor vehicles are the likely source of emissions. With the exception of Cr, Cu, and Zn, most of the airborne heavy metal concentrations determined for impactor samples deviate slightly from the results for total airborne dust. Heavy metal particle size distributions can be divided into three groups. For metals such as As, Cd, Pb, and V, the main fraction can be found in fine particles with a diameter of <2.1 microm, whereas Ce, Cr, Co, and Ni occur mainly in coarse particles with a diameter of >2.1 microm. Cu, Mn, Sb, Zn, Pt, Pd, and Rh occur in high concentrations in the medium range of the impactor stages (particle diameters of 1.1-4.7 microm). Metal concentrations in fine dust particles are needed to assess the human health risks of their inhalation.     

Comparison of the most odour-active volatiles in different hop varieties by application of a comparative aroma extract dilution analysis

Application of a comparative aroma extract dilution analysis on the volatiles isolated from five different hops (Hallertau Perle, Hallertau Hersbrucker Spät, Slowenian Golding, Hallertau Smaragd, US Cascade) revealed linalool and myrcene with the highest Flavour Dilution (FD)-factors in all varieties, followed by 2-isopropyl-3-methoxypyrazine, 3-methylbutanoic acid and geraniol. Some odourants, however, showed high FD-factors only in certain varieties, for example, (5Z)-octa-1,5-dien-3-one and germacrene B in Hersbrucker Spät, (3E,5Z)-undeca-1,3,5-triene in Hersbrucker Spät and Cascade and nonanal in Cascade. The overall odour profile of the Cascade sample clearly differed from the other varietes, and was dominated by a black currant like odour note. The identification experiments revealed 4-methyl-4-sulfanylpentan-2-one, so far unknown as hop constituent, as key contributor to this odour. In addition, an odour-active undecatetraene was present, in particular, in Perle and Cascade. Synthesis and structural assignment of the four stereoisomers of (3E)-undeca-1,3,5,9-tetraene allowed the identification of the fresh, pineapple-like smelling compound as (3E,5Z,9E)-undeca-1,3,5,9-tetraene. Among the four isomers synthesised, this compound showed by far the lowest odour threshold of 0.01 ng/L in air.     

Effect of acid deposition on quantity and quality of dissolved organic matter in soil-water

The aim of this study was to explore how acid deposition may affect the concentration and quality of dissolved organic matter (DOM) in soil-water. This was done by a small-scale acidification experiment during two years where 0.5 × 0.5 m(2) plots were artificially irrigated with water with different sulfuric acid content, and soil-water was sampled using zero-tension lysimeters under the O-horizon. The DOM was characterized using absorbance, fluorescence, and size exclusion chromatography analyses. Our results showed lower mobility of DOM in the high acid treatment. At the same time, there was a significant change in the DOM quality. Soil-water in the high acid treatment exhibited DOM that was less colored, less hydrophobic, less aromatic, and of lower molecular weight, compared to the low acid treatment. This supports the hypothesis that reduction in sulfur deposition is an important driver behind the ongoing brownification of surface waters in many regions.