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      • Synthesis of Functional Block Copolymers Carrying One Poly(<i>p</i>-phenylenevinylene) and One Nonconjugated Block in a Facile One-Pot Procedure

        Menk, Florian,Shin, Suyong,Kim, Kyung-Oh,Scherer, Martin,Gehrig, Dominik,Laquai, Fré,dé,ric,Choi, Tae-Lim,Zentel, Rudolf American Chemical Society 2016 Macromolecules Vol.49 No.6

        <P>Block copolymers composed of a MEH-PPV block and a nonconjugated functional block (molecular weights between 5 and 90 kg/mol) were synthesized in a facile one-pot procedure via ROMP. This one-pot procedure permits the synthesis of numerous block copolymers with little effort. Amphiphilic block copolymers were obtained via incorporation of oxanorbornene carrying, a PEG side chain as well as via postpolymerization modification of a reactive ester carrying norbornene derivative with methoxypoly(ethylene glycol)amine. These amphiphilic block copolymers can be self-assembled into micelles exhibiting different sizes (60-95 nm), morphologies (micelles or fused, caterpillar-like micelles), and optical properties depending on the polymer composition and the micellization procedure. Furthermore, the reactive ester carrying block copolymers enabled the introduction of anchor groups which facilitated the preparation of nanocomposites with CdSe/CdZnS core shell QDs. The obtained composites were studied using time-resolved photoluminescence measurements. The results revealed an increased interaction based on an accelerated decay of the QD emission for composites as compared to the mixture of the QDs with unfunctionalized polymers.</P>

      • Quantitative detection of changes in the leaf-mesophyll tonoplast proteome in dependency of a cadmium exposure of barley (Hordeum vulgare L.) plants

        Schneider, Thomas,Schellenberg, Maja,Meyer, Stefan,Keller, Felix,Gehrig, Peter,Riedel, Kathrin,Lee, Youngsook,Eberl, Leo,Martinoia, Enrico WILEY-VCH Verlag 2009 Proteomics Vol.9 No.10

        <P>Although the vacuole is the most important final store for toxic heavy metals like cadmium (Cd<SUP>2+</SUP>), our knowledge on how they are transported into the vacuole is still insufficient. It has been suggested that Cd<SUP>2+</SUP> can be transported as phytochelatin-Cd<SUP>2+</SUP> by an unknown ABC transporter or in exchange with protons by cation/proton exchanger (CAX) transporters. To unravel the contribution of vacuolar transporters to Cd<SUP>2+</SUP> detoxification, a quantitative proteomics approach was performed. Highly purified vacuoles were isolated from barley plants grown under minus, low (20 μM), and high (200 μM) Cd<SUP>2+ </SUP>conditions and protein levels of the obtained tonoplast samples were analyzed using isobaric tag for relative and absolute quantitation (iTRAQ™). Although 56 vacuolar transporter proteins were identified, only a few were differentially expressed. Under low-Cd<SUP>2+</SUP> conditions, an inorganic pyrophosphatase and a γ-tonoplast intrinsic protein (γ-TIP) were up-regulated, indicating changes in energization and water fluxes. In addition, the protein ratio of a CAX1a and a natural resistance-associated macrophage protein (NRAMP), responsible for vacuolar Fe<SUP>2+</SUP> export was increased. CAX1a might play a role in vacuolar Cd<SUP>2+</SUP> transport. An increase in NRAMP activity leads to a higher cytosolic Fe<SUP>2+</SUP> concentration, which may prevent the exchange of Fe<SUP>2+</SUP> by toxic Cd<SUP>2+</SUP>. Additionally, an ABC transporter homolog to AtMRP3 showed up-regulation. Under high Cd<SUP>2+</SUP> conditions, the plant response was more specific. Only a protein homologous to AtMRP3 that showed already a response under low Cd<SUP>2+</SUP> conditions, was up-regulated. Interestingly, AtMRP3 is able to partially rescue a Cd<SUP>2+</SUP>-sensitive yeast mutant. The identified transporters are good candidates for further investigation of their roles in Cd<SUP>2+</SUP> detoxification.</P>

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