Synthesis of fused polycycles by 1,4-palladium migration chemistry

Novel palladium migration/arylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution.     

Spectroscopic ellipsometry study of liquid crystal and polymeric thin films in visible and near infrared

In this work, we propose spectroscopic ellipsometry as a suitable method for measuring optical properties in soft materials, polymers and liquid crystals, specially selected for use in photonics applications. We show the results of our measurements on some multilayered samples, in the range from visible to the near-IR region, of interest for telecom applications. We point out potentialities and limits of the technique and compare the obtained results with another experimental method, the m-lines spectroscopy, and/or with existing data in the literature. The results about the optical parameters for the analysed materials (the nematic liquid crystal 5CB, one commercial and one lab made optical polymer, and an Indium Tin Oxide film) are useful and interesting by themselves. In fact, as a paradigmatic example, we briefly discuss how an incomplete knowledge of this kind of data can lead to a wrong design of a Bragg grating device. However, more than in the provided data, we put the interest of the present analysis in the warnings about spectroscopic ellipsometry utilization and eventually the necessity of getting complementary information.Received: 13 May 2004, Published online: 29 June 2004PACS: 78.20.Ci Optical constants (including refractive index, complex dielectric constant, absorption, reflection and transmission coefficients, emissivity) - 78.66.Qn Polymers; organic compounds - 07.60.Fs Polarimeters and ellipsometers     

JE-TROSY: combined J- and TROSY-spectroscopy for the measurement of one-bond couplings in macromolecules

With the application of RDCs in high-resolution NMR studies of macromolecules, there has been an interest in the development of accurate, sensitive methods for measuring 15N-1H and 13C-1H one-bond coupling constants. Most methods for determining these couplings are based on the measurement of the displacement between cross-peak components in J-coupled spectra. However, for large macromolecules and macromolecular complexes, these methods are often unreliable since differential relaxation can significantly broaden one of the multiplet components (i.e., the anti-TROSY component) and thereby make accurate determination of its position difficult. To overcome this problem, a J-evolved transverse relaxation optimized (JE-TROSY) method is presented for the determination of one-bond couplings that involves J-evolution of the sharpest cross-peak multiplet component selected in a TROSY experiment. Couplings are measured from the displacement of the TROSY component in the additional J-evolution dimension relative to a zero frequency origin. The JE-TROSY method is demonstrated on uniformly labeled 15N, 13C-labeled RNA and peptide samples, as well as with an RNA-protein complex, in which the protein is uniformly 15N, 13C-labeled. In all cases, resolved, sensitive spectra are obtained from which heteronuclear one-bond J-couplings could be accurately and easily measured.     

A remark on intersection of convex sets

Let X be a real Banach space. Let be a family of closed, convex subsets of X. We show that either the intersection ?_γ∈Γ(G_γ)^? of the ?-neighborhood of the sets G_γ is bounded for each ?>0, or it is unbounded for each ?>0. From this we derive a fixed point theorem for suitable maps that move some points along a bounded direction in Hilbert spaces.     

The Effect of Platinum on Diffusion Kinetics in β‐NiAl: Implications for Thermal Barrier Coating Lifetimes

Platinum is added to thermal barrier coatings (TBCs) as it is observed empirically to extend their lifetime, but the mechanism by which Pt acts is unknown. Since Pt has been proposed to alter diffusivities in NiAl, a key component of TBCs, we use first‐principles quantum mechanics calculations to investigate atomic level diffusion mechanisms. Here, we examine the effect of Pt on five previously proposed mechanisms for Ni diffusion in NiAl: next‐nearest‐neighbor jumps, the triple defect mechanism, and three variants of the six jump cycle. We predict that Pt increases the rate of Ni diffusion by stabilizing point defects and defect clusters that are diffusion intermediates. Previously, we predicted the triple defect mechanism to be a dominant Ni diffusion mechanism; it simultaneously results in long‐range Al diffusion in the opposite direction. Since Pt increases the rate of Ni diffusion, it also increases Al diffusion in NiAl, which may be key to extending the coating lifetime.     

Diffusion effects on the interfacial tension of immiscible polymer blends

Most methods of measuring the interfacial tension between two immiscible polymers are based on the analysis of the shape that a drop of one polymer immersed in the other one exhibits under the action of flow or gravity. In such a situation, the small, yet nonzero mutual solubility between the two polymers acts toward mass transfer between the drop and the surrounding fluid. In this work, diffusion effects on the interfacial tension of the pair polyisobutylene/polydimethylsiloxane have been investigated by drop deformation under shear flow. When the drop was made of polyisobutylene, drop size decreased with time due to diffusion. Drop shrinkage was associated with a significant increase in interfacial tension, until an apparent plateau value was reached. The effect was attributed to a selective migration of molecular weights, which would act to enrich the drop with higher molar mass material. To support such an interpretation, drop viscosity was evaluated by drop shape analysis and it was actually found to increase with time. In some cases, the ratio between drop and continuous phase viscosity became higher than the critical value for drop breakup in shear flow. Upon inverting the phases (i.e., when the drop was made of polydimethylsiloxane), no significant transient effects were observed. In the light of these results, the problem of what are the correct values of interfacial tension and viscosity ratio for a polymer blend of a certain composition will also be discussed. Received: 25 January 1999 Accepted: 24 May 1999     

Experimental investigation of ice slurry flow pressure drop in horizontal tubes

Pressure drop behaviour of ice slurry based on ethanol–water mixture in circular horizontal tubes has been experimentally investigated. The secondary fluid was prepared by mixing ethyl alcohol and water to obtain initial alcohol concentration of 10.3% (initial freezing temperature ?4.4 °C). The pressure drop tests were conducted to cover laminar and slightly turbulent flow with ice mass fraction varying from 0% to 30% depending on test conditions. Results from flow tests reveal much higher pressure drop for higher ice concentrations and higher velocities in comparison to the single phase flow. However for ice concentrations of 15% and higher, certain velocity exists at which ice slurry pressure drop is same or even lower than for single phase flow. It seems that higher ice concentration delay flow pattern transition moment (from laminar to turbulent) toward higher velocities. In addition experimental results for pressure drop were compared to the analytical results, based on Poiseulle and Buckingham–Reiner models for laminar flow, Blasius, Darby and Melson, Dodge and Metzner, Steffe and Tomita for turbulent region and general correlation of Kitanovski which is valid for both flow regimes. For laminar flow and low buoyancy numbers Buckingham–Reiner method gives good agreement with experimental results while for turbulent flow best fit is provided with Dodge–Metzner and Tomita methods.Furthermore, for transport purposes it has been shown that ice mass fraction of 20% offers best ratio of ice slurry transport capability and required pumping power.