Effect of reaction conditions on the molecular weight and polydispersity of linear poly(arylene ether phosphine oxide)s prepared from an AB monomer

A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via ¹H, ¹³C, and ³¹P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, M_n, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using ³¹P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with T_d (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006     

IN VIVO INDUCTION OF 4-THIOURIDINE-CYTIDINE ADDUCTS IN tRNA OF E. COLI B/r BY NEAR-ULTRAVIOLET RADIATION*

Abstract— Near-ultraviolet (near-UV; 320–405 nm) irradiation of Escherichia coli B/r induces the formation in vivo of ⁴Srd-Cyd adducts in transfer RNA, as evidenced by (1) fluorescence spectrum changes of tRNA extracted from irradiated cells and reduced with NaBH₄, (2) thin-layer chromatography on cellulose of hydrolysates of trichloroacetic acid-precipitable extracts of irradiated cells, and (3) comparison of these findings with adduct formation induced by near-UV irradiation of purified mixed tRNA from E. coli. The kinetics of induction of the ⁴Srd-Cyd adduct in vivo, and the near-UV fluences required, provide strong support for our earlier hypothesis that formation of these adducts is responsible for near-UV-induced growth delay in E. coli.     

Surface structuring of particle laden drops using electric fields

Emulsion drops readily adsorb particles at their surfaces, which may lead to a fluid or solid layer encapsulating the drop, known as an armored drop. In this review, we discuss how electric fields can be used to manipulate colloidal surface structures, by dielectrophoretic or electro-hydrodynamic mechanisms and we also compare this to related phenomena in lipid bilayer vesicles. The phenomena discussed are important for a wide range of uses of particle laden drops, including emulsion stabilization, Janus or patchy mesocapsule-, scaffold- or other materials-production.     

Poly(arylene ether)s with pendant diphenyl phosphoryl groups: Synthesis,characterization, and thermal properties

A series of poly(arylene ether)s, (PAEs), carrying a pendant diphenyl phosphoryl group were prepared via the nucleophilic aromatic substitution (NAS) reactions of 3,5‐difluorotriphenylphosphine oxide, 6 . The difluoro monomer 6 was synthesized via two‐step reaction sequence and subsequently characterized by ¹H, ¹³C, ¹⁹F, and ³¹P NMR spectroscopy, GC/MS, and elemental analysis. The reactivity of the electrophilic sites in 6 , activated by only a diphenylphosphoryl group located in the meta‐position, in 6 was probed via NMR spectroscopy and model reactions and was determined to be sufficient to undergo typical NAS reactions. High molecular weight, amorphous, organic soluble poly(arylene ether)s, bearing a pendant diphenylphosphoryl group, were prepared via the reaction of 6 with a variety of bis‐phenols under typical NAS conditions. The poly(arylene ether)s were characterized for structure via the use of ¹H, ¹³C, and ³¹P NMR spectroscopy while their thermal properties were evaluated using DSC and TGA analysis. The glass transition temperatures (T_g) of the synthesized PAEs ranged from 143 to 175 °C, while their 5% weight loss temperatures ranged from 467 to 510 °C under nitrogen and from 470 to 526 °C in air. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Analysis of vibrating-wire stress gage in soft rock

An analysis for the in situ elastic response of a vibrating-wire stress gage in soft rock (E<10⁵ Mpa) has been accomplished with the use of the finite-element method and approximate analytical procedures. The vibrating-wire stress gage is not a true stressmeter in that it is somewhat dependent on rock-modulus changes. Conventional procedures for calibration include the assumption that this dependency is linear with respect to rock modulus. In this analysis, a nonlinear relationship is demonstrated and an approximate mathematical expression is derived for it. Good agreement is obtained between theoretical calibration factors and test results on laboratory-scale samples with the stressmeter.     

Flow of clays

Recent experimental and theoretical research into physical phenomena in clays is reviewed. Clays’ present place in the context of modern materials science is briefly discussed, and illustrated through the rich behavior recently displayed in this physical model system. We will show that in order to understand macroscopic flow behaviors in these systems, it is crucial to know the underlying nanostructures in detail. With the clay nanostructural basis at hand, we will review recent advances in clay systems from the geological example of quick clay flows and avalanches, to materials science and the stability, strength and flow of smart electrorheological clay structures. In the case of natural quick clay, there is now hope of establishing a protocol for avalanche preditction based on rheological sample data. In materials science, the use of electric fields together with flow in order to improve the processing of clay composite materials may open new unexplored avenues. We will finally discuss that due to the interplay of van der Waals and electrostatic forces screened by ions at the nanoscale, clays may either form a glass, or a gel and thus give fundamental insights into the elusive questions related to materials universal aging flow dynamics.     

REDUCTION BY NEAR-ULTRAVIOLET (334 nm) LIGHT OF E. COLI CAPACITY FOR PHAGE GROWTH DEPENDS UPON THE rel GENE AND 4-THIOURIDINE

Abstract— Near-ultraviolet radiation (near UV; 300–380 nm) has long been known to produce a transient reduction of the capacity of bacteria to support phage growth. The present work shows that, at high fluenœs (40–100 kJ/m²), 85% of 334-nm-induced reduction of capacity in Escherichia coli B/r requires the rel gene; that is, it results from rel -gene activity caused by the near-UV treatment. This rel -gene activity leads to (1) a bacterial growth delay and concomitantly lowered bacterial metabolism, and (2) a parallel delay in phage development, with a considerable depression of burst size. We propose that the observed effects on phage development are a consequence primarily of the lowered bacterial metabolism, but they may also result partly from a direct inhibition of phage DNA synthesis by the rel gene product, these effects together leading to the observed reduction of capacity in a rel ⁺ strain. The remaining 15% of capacity reduction, observed in a rel strain, has an unknown mechanism, but does appear to involve a delay in phage development.
At least 95% of the total capacity reduction observed in the rel ⁺ strain in the range 40–100 kJ/m² requires the presence of 4-thiouridine, an unusual base in E. coli transfer RNA, which is presumably both the chromophore and the target for near-UV-induced capacity reduction.