Temporal trends, congener patterns, and sources of octa-, nona-, and decabromodiphenyl ethers (PBDE) and hexabromocyclododecanes (HBCD) in Swiss lake sediments

With the recent ban of pentabromodiphenyl ether (technical PentaBDE) and octabromodiphenyl ether (technical OctaBDE) mixtures in the European Union (EU) and in parts of the United States, decabromodiphenyl ether (technical DecaBDE) remains as the only polybrominated diphenyl ether (PBDE) based flame retardant available, today. The EU risk assessment report for DecaBDE identified a high level of uncertainty associated with the suitability of the current risk assessment approach for secondary poisoning by debromination of DecaBDE to toxic lower brominated diphenylethers. Addressing this still open question, we investigated concentrations and temporal trends of DecaBDE, NonaBDE, and OctaBDE congeners in the sediments of Greifensee, a small lake located in an urban area close to Zürich, Switzerland. PBDE appeared first in sediment layers corresponding to the mid 1970s. While total Tri-HeptaBDE (BDE-28, -47, -99, -100, -153, -154 and -183) concentrations leveled off in the mid 1990s to about 1.6 ng/g dw (dry weight), DecaBDE levels increased steadily to 7.4 ng/g dw in 2001 with a doubling time of 9 years. Hexabromocyclododecanes (HBCD) appeared in Greifensee sediments in the mid 1980s. They are an important class of flame retardants that are being used in increasing amounts, today. As was observed for DecaBDE, HBCD concentrations were continuously increasing to reach 2.5 ng/g dw in 2001. Next to DecaBDE, all 3 NonaBDE congeners (BDE-208, BDE-207, and BDE-206) and at least 7 out of the 12 possible OctaBDE congeners (BDE-202, BDE-201, BDE-197/204, BDE-198/203, BDE-196/200, BDE-205, and BDE-194) were detected in the sediments of Greifensee. Highest concentrations were found in the surface sediments with 7.2, 0.26, 0.14, and 1.6 ng/g dw for Deca-, Nona-, Octa-, and the sum of Tri-HeptaBDE, respectively. While DecaBDE and NonaBDE were found to increase rapidly, the increase of OctaBDE was slower. Congener patterns of Octa- and NonaBDE present in sediments of Greifensee did not change with time. Consequently, there was no evidence for sediment mediated long-term transformation of PBDE within the observed time span of almost 30 years. Despite the high persistence of DecaBDE, environmental debromination occurs, as shown by the detection of a shift in congener patterns of Octa- and NonaBDE in sediments, compared to the respective congener patterns in technical PBDE products. The OctaBDE congener BDE-202 was detected in sediments, representing a transformation product that is not reported in any of the technical PBDE products. Comparison of OctaBDE congener patterns in sediments with OctaBDE congener patterns from known sources reveals that (i) they were distinctively different from the congener patterns in technical PBDE products and (ii) that they were similar to the OctaBDE patterns in house dust and photodegradation products of DecaBDE, suggesting contributions from these sources.     

A non-conserved sequence in the 5'region of the CYH2 intron from Saccharomyces cerevisiae controls splicing efficiency of the pre-mRNA

The CYH2 gene from Saccharomyces cerevisiae containing one 510 bp intron is spliced inefficiently. We have shown previously that a non-conserved sequence within the intron is responsible for this low splicing efficiency. Using synthetic oligonucleotides comprising the identified region we show in this report that a very short region contains the specificity to act negatively on the splicing efficiency of the CYH2 gene. Furthermore, this sequence influences the splicing efficiency only when it is placed close to the 5' splice site of the gene. Investigations with chimeric CYH2/beta-actin genes show that this sequence acts independent from its natural surroundings. We propose that this sequence might interact with splicing factor(s).     

Ein Beitrag zur Biosynthese amylosereicher Erbsenstärken

Contribution to the Biosynthesis of High-amylose Pea Starches Biosynthesis of starch is a complex process but few details are still unknown. This paper describes an investigation upon pea starch biosynthesis. Peas as a source of starch offer two qualities, a pea starch with 40% amylose content (smooth pea starch) and a pea starch with more than 60% amylose content (wrinkled pea starch). Samples for analysis were taken during growth. According to the quantitative determination of starch and amylose the accuracy of amylose detection was tested. Furthermore a qualitative analysis was carried out by molecular weight estimation of the starch. Both kinds of peas showed a high amylose synthesis during the last few days of growth, whereas amylopectin synthesis was highly in earlier stages. Wrinkled peas have shown only little synthesis activity of amylopectin during maturity. Therefore the amylose content of these peas was higher, instead of equal amylose synthesis quotas of both smooth and wrinkled peas.     

Inhibitory effects of trans-resveratrol analogs molecules on the proliferation and the cell cycle progression of human colon tumoral cells

Resveratrol may function as a cancer chemopreventive agent. However, few data are available on the antitumoral activities of its dimer, epsilon-viniferin, also present in human diet. So, the effects of resveratrol, epsilon-viniferin, of their acetylated forms (resveratrol triacetate, epsilon-viniferin pentaacetate) and of vineatrol (a wine grape extract) were compared on human adenocarcinoma colon cells. Resveratrol and resveratrol triacetate inhibit cell proliferation and arrest cell cycle. epsilon-Viniferin and epsilon-viniferin pentaacetate slightly reduce cell proliferation. Vineatrol inhibits cell proliferation and favors an accumulation in the S phase of the cell cycle. Consequently, resveratrol triacetate and vineatrol could constitute new putative anticancer agents on colon carcinoma.     

Non-fickian diffusion with reaction in glassy polymers with swelling induced by the penetrant—effects of consecutive and parallel reactions

A mathematical model is presented for non-Fickian diffusion of a penetrant A into a granular glassy polymer containing a reactive group B, resulting in the desired product P. Further, both a consecutive reaction between A and P (producing X) and a parallel reaction between A and C (producing Y) are incorporated, with C initially present in the particle. The swelling of the polymer, induced by the penetrant, is described by power-law kinetics for the velocity of the swelling front. Kinetics are considered to be first order in each of the two reactants. Concentration profiles in the particle and selectivity to desired product are calculated as function of the swelling behavior of the polymer grain. In case of a consecutive reaction the local concentration of P reaches a maximum value independent of the swelling rate. However, the position of the maximal concentration of P moves towards the center of the grain with a rate depending on the kinetics of swelling. For Case II diffusion this velocity equals the velocity of the advancing front between glassy and rubbery polymer. The selectivity of the desired reaction decreases with decreasing swelling rate. A low swelling rate also results in an inhomogeneous product distribution within the granule. A criterion is derived predicting under what conditions the consecutive reaction can be neglected and a pure product is obtained. The analysis further reveals that both a more homogeneous product and a higher selectivity toward a desired product can be obtained by realizing preswelling of the polymer with an inert swelling agent. For Case II diffusion the concentration profiles of the side product of the parallel reaction, Y, are flat in the rubbery part of the polymer. This is caused by the relatively low swelling rate allowing Y to redistribute in the swollen polymer. If additional C is continuously supplied from the gas phase, then the selectivity decreases continuously with increasing conversion of B.     

Untersuchungen zur Amylosebestimmung in proteinreichen Stärkerohstoffen,insbesondere Erbsen

Investigations on the Amylose Determination in High Protein Starch Source Materials, Especially Peas. The proposed utilization of amylose rich starches requires different methods of amylose determination. In addition to laboratory methods also simple tests are important to that. Because the discussed legume starches are hardly investigated, first of all the suitability of the amperometric iodine titration had to be checked. Then a more easier work was described. In the case of routine analyses a modified test procedure was compared with the method of iodine titration.     

Polymerization of cyclic monomers. VII. Synthesis and radical polymerization of 1,3‐bis[(1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzenes

1,3‐Bis[(1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzenes 1 [RO: CH₃O (a), C₂H₅O (b)] were synthesized by the esterification of the corresponding 1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐carboxylic acids with resorcinol. The structure of the new vinylcyclopropanes was confirmed by elemental analysis and infrared (IR), ¹H nuclear magnetic resonance (¹H‐NMR), and ¹³C nuclear magnetic resonance (¹³C‐NMR) spectroscopy. The radical polymerization of difunctional 2‐vinyl‐cyclopropanes in bulk with 2,2′‐azoisobutyronitrile (AIBN) results in hard, transparent, crosslinked polymers. During the bulk polymerization of the crystalline bis[(1‐methoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzene 1a, an expansion in volume of about 1% took place. The radical solution polymerization of 1a resulted in a soluble polymer with pendant 2‐vinylcyclopropane groups. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1775–1782, 1999