Synthesis and characterization of the first fluorescent nonpeptide NPY Y1 receptor antagonist

Cyanine-5-labelled neuropeptide Y (NPY) was demonstrated to be an ideal universal fluorescent ligand for the combined investigation of NPY Y(1), Y(2) and Y(5) receptors. With respect to improved stability, detection of receptor subtypes in cells and tissues, and prevention of receptor internalization, small nonpeptidic fluorescent antagonists should be superior. Here we present a set of four fluorescent nonpeptide NPY Y(1) receptor (Y(1)R) antagonists. The highest affinity was obtained by labelling an N(G)-(6-aminohexanoyl)argininamide derived from the Y(1)R antagonist BIBP 3226, with Py-1, a small pyrylium dye. The fluorescent pyridinium-type Y(1)R antagonist, compound 4 had K(i) values of 29 nM and 2.7 nM, which were determined by radioligand binding and flow cytometry under equilibrium conditions, respectively; 4 had a K(b) value of 0.6 nM (Ca(2+) assay). The large Stoke's shift (541 vs. 615 nm) in buffer (PBS, pH 7.4) in the presence of 1% BSA and the red emission (quantum yield 56%) are advantageous with respect to the signal-to-noise ratio. The new probe was successfully used in fluorescence-based binding experiments evaluated by flow cytometry and confocal microscopy; this demonstrates the potential of pyrylium dyes for the preparation of fluorescent ligands that are applicable for the study of G protein-coupled receptors on living cells.     

Unambiguous atomic structural determination of single-walled carbon nanotubes by electron diffraction

We introduce a novel non-dimensional “intrinsic layer-line spacing” concept for electron diffraction analysis of single-walled carbon nanotubes (SWCNTs). Accordingly, we develop a unique method for direct determination of chiral indices (n, m) of the carbon nanotubes from their electron diffraction patterns (EDPs). The new method is totally calibration-free. Errors due to the nanotube inclination are specified. The tilt angle of the carbon nanotube with respect to the incident electron beam is simultaneously evaluated, thus the effect of the tube tilting is compensated for in the (n, m) determination. Several effective procedures are proposed to cross-check the results by using abundant information contained in the diffraction patterns. The efficiency of the method is demonstrated on both simulated and experimental diffraction patterns from single-walled nanotubes. The technique can be extended to structural analysis of nanotubes of structure similar to carbon nanotubes, such as boron nitride nanotubes.     

Technical and Economical Aspects of Current Thermal Barrier Coating Systems for Gas Turbine Engines by Thermal Spray and EBPVD: A Review

The most advanced thermal barrier coating (TBC) systems for aircraft engine and power generation hot section components consist of electron beam physical vapor deposition (EBPVD) applied yttria-stabilized zirconia and platinum modified diffusion aluminide bond coating. Thermally sprayed ceramic and MCrAlY bond coatings, however, are still used extensively for combustors and power generation blades and vanes. This article highlights the key features of plasma spray and HVOF, diffusion aluminizing, and EBPVD coating processes. The coating characteristics of thermally sprayed MCrAlY bond coat as well as low density and dense vertically cracked (DVC) Zircoat TBC are described. Essential features of a typical EBPVD TBC coating system, consisting of a diffusion aluminide and a columnar TBC, are also presented. The major coating cost elements such as material, equipment and processing are explained for the different technologies, with a performance and cost comparison given for selected examples.     

Direct synthesis of hydrogen peroxide from H2 and O2 using zeolite-supported Au catalysts

The direct synthesis of hydrogen peroxide from H₂ and O₂ using zeolite-supported Au catalysts is described and their activity is contrasted with silica- and alumina-supported Au catalysts. Two zeolites were investigated, ZSM-5 and zeolite Y. The effect of calcination of these catalysts is studied and it is found that for uncalcined catalysts high rates of hydrogen peroxide formation are observed, but these catalysts are unstable and lose Au during use. Consequently, reuse of these catalysts leads to lower rates of hydrogen peroxide formation. However, catalysts calcined at 400 °C are more stable and can be reused without loss of gold. The use of zeolites as a support for Au gives comparable rates of hydrogen peroxide formation to alumina-supported Au catalysts and higher rates when compared with silica-supported catalysts. prepared using a similar method. Zeolite Y-supported catalysts are more active than ZSM-5-supported catalysts for the stable calcined materials. It is considered that the overall activity of these supported catalysts may be related to the aluminium content as the activity increases with increasing aluminium content.     

Solvent-free oxidation of benzyl alcohol with oxygen using zeolite-supported Au and Au–Pd catalysts

The oxidation of benzyl alcohol to benzaldehyde has been investigated in the absence of solvent using zeolite-supported Au and Au–Pd catalysts. Three zeolites were investigated, ZSM-5, zeolite β and zeolite Y, and these were contrasted with the titanoslicalite TS-1 and TiO₂ as supports. For the Au catalysts the best results are obtained with zeolite β as the support and the conversions were comparable or better than those observed with TiO₂ in terms of turn over frequencies. However, the selectivities observed with the acidic zeolites were lower than the non-acidic TS-1 and TiO₂. This is due to the subsequent reaction of benzaldehyde via acid catalysed reactions to give benzyl benzoate and its dibenzyl acetal, and, in some cases dibenzylether. Initial catalysts were evaluated with a gold loading of 2 wt% and increasing this to 4 wt% showed the expected increase in activity, indicating that there is scope to improve the performance of these catalysts. The most active catalysts were prepared by impregnation and catalysts prepared by deposition precipitation were considerably less active. Introduction of Pd into the catalyst improved the activity without significantly affecting the selectivity.     

Prediction of foam growth and its nucleation in free and limited expansion

The influence volume approach (IVA) is often utilized for modeling the mass transfer process dictating bubble growth dynamics in physical foaming. However, the assumed concentration profile in the IVA method is only valid when the changes in dissolved gas concentration are small (less than 5%). In addition, the validity of the IVA method is difficult to justify in chemical foaming applications because of the difficulties involved in defining the dissolved gas concentration profile.In the present work, we define two distinct stages of bubble growth for physical foaming. These two stages are termed as free and limited expansion and are controlled by the bubble nucleation rate. Bubble nucleation is assumed to occur only in the free expansion stage. In this stage, the bubble pressure drops substantially from an initially high pressure in the supersaturated state while the dissolved gas concentration changes very little. The second stage of our two-stage mass transfer model is termed the limited expansion stage and accounts for bubble growth in the late stages of foam evolution, when the pressure changes become small. However, in the limited stage of bubble growth the dissolved gas concentration drops significantly, as the available dissolved gas is depleted. To summarize our two-stage mass transfer model of foam expansion, the pressure difference between the bubble phase and the liquid phase is the primary mechanism for driving mass transfer in the early (free) stages of foam growth and the concentration difference is the driver for bubble growth in the late (limited) stages of growth. The first stage can be regarded as the nucleation stage and it is relatively short; while the second stage can be regarded as the bubble growth stage and is much longer. Most of the bubble volume expansion takes place in the second stage.The concentration gradient at the bubble edge, which is often ignored in other models, is analyzed in detail in this paper. The details of our novel mass transfer model are also presented.     

Single-walled carbon nanotube synthesis using ferrocene and iron pentacarbonyl in a laminar flow reactor

A gas-phase process of single-walled carbon nanotube (SWCNT) formation, based on thermal decomposition of iron pentacarbonyl or ferrocene in the presence of carbon monoxide (CO), was investigated in ambient pressure laminar flow reactors in the temperature range of 600-1300 °C. Ferrocene was found to be a better catalyst precursor in the studied conditions since iron pentacarbonyl decomposes at lower temperatures resulting in the excessive growth of catalyst particles. In situ sampling carried out at 1000 °C showed that the SWCNT growth occurred from individual metal particles in the heating section of the furnace in the temperature range of 891-928 °C, in which the growth rate was estimated to exceed . FT-IR measurements of gaseous products revealed that the majority of the CO disproportionation took place on the reactor walls. Raman measurements confirmed the results of TEM observations, namely, the formation of very high purity SWCNT product. On-line aerosol number size distributions were measured to detect the conditions of SWCNT formation and the product morphology changes. Mechanism of SWCNT formation in the gas phase from ferrocene and CO is discussed.     

Avalanching flow of cohesive powders

The flow dynamics of cohesive powders is investigated in rotating cylinders with an L : R ratio of 3 : 1 using experiments and DEM simulations. Flow onset and steady-state behavior are compared for free-flowing (cohesionless) dry glass beads, wet glass beads, and “dry” cohesive powders (lactose, microcrystalline cellulose). The avalanching dynamics of powders is substantially different from those observed for free-flowing or wet-cohesive glass beads. Dry cohesive powders exhibit history-dependent flow dynamics, significant dilation, aperiodic avalanche frequencies, and variable avalanche size. These behaviors also provide a route for effective characterization of cohesive forces under dilated conditions characteristic of unconfined flows.     

Polyethylene Glycol as an Environmentally Friendly and Recyclable Reaction Medium for Enantioselective Hydrogenation

Polyethylene glycol (PEG) was found to be an inexpensive, non‐toxic and recyclable reaction medium for ruthenium‐ and rhodium‐catalyzed asymmetric hydrogenation of 2‐arylacrylic acids (Ru‐catalyzed CC bond reduction), enamides (Rh‐catalyzed CC bond reduction), β‐keto esters and simple aromatic ketones (Ru‐catalyzed CO bond reduction). In all cases, high catalytic activities and enantioselectivities have been achieved, which are comparable to those obtained in conventional organic solvent systems. The Ru and Rh catalysts prepared with commercially available chiral diphosphine ligands could be readily recycled by simple extraction, as in the case of ionic liquids, and reused up to nine times without obvious loss of catalytic activity and enantioselectivity. The reduced products were obtained from the extracts in high isolated yields. These results indicate that PEGs as new reaction media are attractive alternatives to room temperature ionic liquids.     

Contact dynamic modeling of a liquid droplet between two approaching porous materials

A computational fluid dynamics model based on a finite difference solution to mass and momentum conservation equations (Navier–Stokes equations) for a liquid droplet transport between two porous or nonporous contacting surfaces (CSs) is developed. The CS dynamic (equation of motion) and the spread of the incompressible liquid available on the primary surface for transfer are coupled with the Navier–Stokes equations. The topologies of the spread dynamic between and inside both surfaces (primary and CSs) are compared with experimental data. The amount of mass being transferred into the CS, predicted by the model, is also compared to the experimental measurements. The impact of the initial velocity on the spread topology and mass transfer into the pores is addressed. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2346–2353, 2014