Synthesis of Diblock and Triblock Polymers from Cyclooctadiene and Norbornene Via ROMP in Miniemulsion.

The synthesis of diblock and triblock linear polyolefins via ring opening metathesis polymerization (ROMP) in an aqueous nanoparticle dispersion is presented. The different block polyolefins are synthesized from the cyclic olefins 1,5-cyclooctadiene and norbornene (NB), using a water-soluble TEGylated ruthenium alkylidene catalyst, yielding the structures PCOD-b-PNB, PNB-b-PCOD, and PCOD-b-PNB-b-PCOD. High monomer conversion (>90%), monitored by NMR, is achieved in relatively short times (≈1 h) for the polymerization of each block. The livingness of the system, essential to obtain block copolymers, is confirmed by gel permeation chromatography. Latex particles' size during the multiple steps range between 90 and 150 nm. The results demonstrate that it is possible to obtain nanoparticle latexes from ROMP-based monomers with block copolymer architectures, creating the opportunity to copolymerize olefins bearing different functional groups for the synthesis of new materials.

Polymerization-Induced Self-Assembly (PISA) of 1,5-Cyclooctadiene Using Ring Opening Metathesis Polymerization.

Ring opening metathesis polymerization (ROMP) is a technique that allows the synthesis of well-defined linear polyolefins. Polymerization-induced self-assembly (PISA) involves the synthesis of amphiphilic block copolymers: a hydrophilic block is first polymerized homogeneously in solution (usually water) followed by polymerization of a second hydrophobic block, resulting in a diblock copolymer that self-assembles. In this communication, preliminary results of the development of PISA for the synthesis of amphiphilic block linear polyolefins via ROMP using a water-soluble PEGylated ruthenium alkylidene catalyst are presented. In the first step, a water-soluble modified-norbornene monomer was polymerized in water, then 1,5-cyclooctadiene was added to the system to produce amphiphilic block polyolefins. By varying the concentrations of hydrophilic versus hydrophobic monomer, stable latexes with final particles of ≈200 nm diameter were prepared.

Regional variation in coronary heart disease mortality trends in Portugal, 1981-2012.

BACKGROUND: Information is scarce about the geographic variation in time trends of mortality from coronary heart disease (CHD). We aimed to describe trends in death rates, absolute number of deaths and years of life lost (YLL) due to CHD among men and women in Portugal, by region, from 1981 to 2012. METHODS: The age-standardized mortality rates from CHD were estimated by sex and region. We used joinpoint regression analysis to calculate the annual percent change (APC) in mortality and to identify points of significant change in the trend. The YLL due to premature mortality for CHD were computed using the Global Burden of Disease method. RESULTS: The age-adjusted mortality from CHD decreased between 1981 and 2012, both in men and women, but with significantly different APC by region. Smaller declines in rates were observed in Alentejo (men: APC 1993-2012: -2.4%; women: APC 1991-2012: -2.4%). The greatest decline was observed in Madeira between 2003 and 2012, in men (APC: -7.6%) and women (APC: -9.7%). The decline in rates in Algarve started only after 2003, whereas it was consistent from 1981 in the North and started in the 1990s in most other regions. A decrease in the number of deaths was only observed after 2000. The YLL from CHD decreased from 1981 to 2012, mainly after 2000. CONCLUSIONS: In Portugal, between 1981 and 2012, relative declines of CHD mortality indicators were different by geographic region. Consistent decreases in mortality rates were only observed in the Centre, Lisbon and North, the most populated and urbanized regions.

The fusarium mycotoxin deoxynivalenol can inhibit plant apoptosis-like programmed cell death.

The Fusarium genus of fungi is responsible for commercially devastating crop diseases and the contamination of cereals with harmful mycotoxins. Fusarium mycotoxins aid infection, establishment, and spread of the fungus within the host plant. We investigated the effects of the Fusarium mycotoxin deoxynivalenol (DON) on the viability of Arabidopsis cells. Although it is known to trigger apoptosis in animal cells, DON treatment at low concentrations surprisingly did not kill these cells. On the contrary, we found that DON inhibited apoptosis-like programmed cell death (PCD) in Arabidopsis cells subjected to abiotic stress treatment in a manner independent of mitochondrial cytochrome c release. This suggested that Fusarium may utilise mycotoxins to suppress plant apoptosis-like PCD. To test this, we infected Arabidopsis cells with a wild type and a DON-minus mutant strain of F. graminearum and found that only the DON producing strain could inhibit death induced by heat treatment. These results indicate that mycotoxins may be capable of disarming plant apoptosis-like PCD and thereby suggest a novel way that some fungi can influence plant cell fate.