Ru-Catalyzed, cis-Selective Living Ring-Opening Metathesis Polymerization of Various Monomers, Including a Dendronized Macromonomer, and Implications to Enhanced Shear Stability

An unsaturated polymer’s cis/trans-olefin content has a significant influence on its properties. For polymers obtained by ring-opening metathesis polymerization (ROMP), the cis/trans-olefin content can be tuned by using specific catalysts. However, cis-selective ROMP has suffered from narrow monomer scope and lack of control over the polymerization (giving polymers with broad molecular weight distributions and prohibiting the synthesis of block copolymers). Herein, we report the versatile cis-selective controlled living ROMP of various endo-tricyclo[4.2.2.0^(2,5)]deca-3,9-diene and various norbornene derivatives using a fast-initiating dithiolate-chelated Ru catalyst. Polymers with cis-olefin content as high as 99% could be obtained with high molecular weight (up to M_n of 105.1 kDa) and narrow dispersity (<1.4). The living nature of the polymerization was also exploited to prepare block copolymers with high cis-olefin content for the first time. Furthermore, owing to the successful control over the stereochemistry and narrow dispersity, we could compare cis- and trans-rich polynorbornene and found the former to have enhanced resistance to shear degradation

Effects of copper nanoparticle exposure on host defense in a murine pulmonary infection model

<p>Abstract</p> <p>Background</p> <p>Human exposure to nanoparticles (NPs) and environmental bacteria can occur simultaneously. NPs induce inflammatory responses and oxidative stress but may also have immune-suppressive effects, impairing macrophage function and altering epithelial barrier functions. The purpose of this study was to assess the potential pulmonary effects of inhalation and instillation exposure to copper (Cu) NPs using a model of lung inflammation and host defense.</p> <p>Methods</p> <p>We used <it>Klebsiella pneumoniae </it>(<it>K.p.</it>) in a murine lung infection model to determine if pulmonary bacterial clearance is enhanced or impaired by Cu NP exposure. Two different exposure modes were tested: sub-acute inhalation (4 hr/day, 5 d/week for 2 weeks, 3.5 mg/m³) and intratracheal instillation (24 hr post-exposure, 3, 35, and 100 μg/mouse). Pulmonary responses were evaluated by lung histopathology plus measurement of differential cell counts, total protein, lactate dehydrogenase (LDH) activity, and inflammatory cytokines in bronchoalveolar lavage (BAL) fluid.</p> <p>Results</p> <p>Cu NP exposure induced inflammatory responses with increased recruitment of total cells and neutrophils to the lungs as well as increased total protein and LDH activity in BAL fluid. Both inhalation and instillation exposure to Cu NPs significantly decreased the pulmonary clearance of <it>K.p.</it>-exposed mice measured 24 hr after bacterial infection following Cu NP exposure versus sham-exposed mice also challenged with <it>K.p </it>(1.4 × 10⁵bacteria/mouse).</p> <p>Conclusions</p> <p>Cu NP exposure impaired host defense against bacterial lung infections and induced a dose-dependent decrease in bacterial clearance in which even our lowest dose demonstrated significantly lower clearance than observed in sham-exposed mice. Thus, exposure to Cu NPs may increase the risk of pulmonary infection.</p

Observation of Scarred Modes in Asymmetrically Deformed Microcylinder Lasers

We report observation of lasing in the scarred modes in an asymmetrically deformed microcavity made of liquid jet. The observed scarred modes correspond to morphology-dependent resonance of radial mode order 3 with their Q values in the range of 10^6. Emission directionality is also observed, corresponding to a hexagonal unstable periodic orbit.Comment: 4 pages, 6 figure

Effective Action and Schwinger Pair Production in Scalar QED

Some astrophysical objects are supposed to have very strong electromagnetic fields above the critical strength. Quantum fluctuations due to strong electromagnetic fields modify the Maxwell theory and particularly electric fields make the vacuum unstable against pair production of charged particles. We study the strong field effect such as the effective action and the Schwinger pair production in scalar QED.Comment: RevTex 6 pages, no figure; Proceedings of APCTP Winter School on Black Hole Astrophysics 2008, Jan 24-29, 200

The potato developer (D) locus encodes an R2R3 MYB transcription factor that regulates expression of multiple anthocyanin structural genes in tuber skin

A dominant allele at the D locus (also known as I in diploid potato) is required for the synthesis of red and purple anthocyanin pigments in tuber skin. It has previously been reported that D maps to a region of chromosome 10 that harbors one or more homologs of Petuniaan2, an R2R3 MYB transcription factor that coordinately regulates the expression of multiple anthocyanin biosynthetic genes in the floral limb. To test whether D acts similarly in tuber skin, RT-PCR was used to evaluate the expression of flavanone 3-hydroxylase (f3h), dihydroflavonol 4-reductase (dfr) and flavonoid 3′,5′-hydroxylase (f3′5′h). All three genes were expressed in the periderm of red- and purple-skinned clones, while dfr and f3′5′h were not expressed, and f3h was only weakly expressed, in white-skinned clones. A potato cDNA clone with similarity to an2 was isolated from an expression library prepared from red tuber skin, and an assay developed to distinguish the two alleles of this gene in a diploid potato clone known to be heterozygous Dd. One allele was observed to cosegregate with pigmented skin in an F1 population of 136 individuals. This allele was expressed in tuber skin of red- and purple-colored progeny, but not in white tubers, while other parental alleles were not expressed in white or colored tubers. The allele was placed under the control of a doubled 35S promoter and transformed into the light red-colored cultivar Désirée, the white-skinned cultivar Bintje, and two white diploid clones known to lack the functional allele of D. Transformants accumulated pigment in tuber skin, as well as in other tissues, including young foliage, flower petals, and tuber flesh

Dual bio-responsive gene delivery via reducible poly(amido amine) and survivin-inducible plasmid DNA

A bioreducible poly(amido amine) (SS-PAA) gene carrier, known as poly (amido-butanol) (pABOL), was used to transfect a variety of cancer and non-cancer cell lines. To obtain cancer-specific transgene expression for therapeutic efficiency in cancer treatment, we constructed survivin-inducible plasmid DNA expressing the soluble VEGF receptor, sFlt-1, downstream of the survivin promoter (pSUR-sFlt-1). Cancer-specific expression of sFlt-1 was observed in the mouse renal carcinoma (RENCA) cell line. pABOL enhanced the efficiency of gene delivery compared to traditional carriers used in the past. Thus, a dual bio-responsive gene delivery system was developed by using bioreducible p(ABOL) for enhanced intracellular gene delivery and survivin-inducible gene expression system (pSUR-sFlt-1 or pSUR-Luc reporter gene) that demonstrates increased gene expression in cancer that has advantages over current gene delivery system

Structural Relaxation, Self Diffusion and Kinetic Heterogeneity in the Two Dimensional Lattice Coulomb Gas

We present Monte Carlo simulation results on the equilibrium relaxation dynamics in the two dimensional lattice Coulomb gas, where finite fraction $f$ of the lattice sites are occupied by positive charges. In the case of high order rational values of $f$ close to the irrational number $1-g$ ($g\equiv(\sqrt{5} -1)/2$ is the golden mean), we find that the system exhibits, for wide range of temperatures above the first-order transition, a glassy behavior resembling the primary relaxation of supercooled liquids. Single particle diffusion and structural relaxation show that there exists a breakdown of proportionality between the time scale of diffusion and that of structural relaxation analogous to the violation of the Stokes-Einstein relation in supercooled liquids. Suitably defined dynamic cooperativity is calculated to exhibit the characteristic nature of dynamic heterogeneity present in the system.Comment: 12 pages, 20 figure

Nuclear S-nitrosylation impacts tissue regeneration in zebrafish

The role of the post-translational modifications in tissue regeneration is still not clearly understood. Here, the authors show that many nuclear proteins change S-nitrosylation state in the regenerating zebrafish tailfin, highlighting the importance of Kdm1a S-nitrosylation in the repair process