Use of cyclopropanols as conformational constraints in RCM

[reaction: see text] Sequential application of the Kulinkovich cyclopropanation of carboxylic esters and RCM of the resulting cis-dialkenyl-tethered cyclopropanols provides an expedient route to functionalized medium-sized carbocycles. Subsequent elaboration of the cyclopropanol functionality, such as one-carbon ring expansion, to afford synthetically useful alpha,beta-enones is also worth noting.     

Multiphysics Simulation Combining Large-Eddy Simulation,Wall Heat Conduction and Radiative Energy Transfer to Predict Wall Temperature Induced by a Confined Premixed Swirling Flame

A multi-physics simulation combining large-eddy simulation, conjugate heat transfer and radiative heat transfer is used to predict the wall temperature field of a confined premixed swirling flame operating under atmospheric pressure. The combustion model accounts for the effect of enthalpy defect on the flame structure whose stabilization is here sensitive to the wall heat losses. The conjugate heat transfer is accounted for by solving the heat conduction within the combustor walls and with the Hybrid-Cell Neumann-Dirichlet coupling method, enabling to dynamically adapt the coupling period. The latter coupling procedure is enhanced to determine statistics (mean, RMS, \(\ldots \)) in a permanent regime accurately and efficiently thanks to an acceleration technique which is derived and validated. The exact radiative heat transfer equation is solved with an advanced Monte Carlo method with a local control of the statistical error. The coupled simulation is carried out with or without accounting for radiation. Excellent results for the wall temperature are achieved by the fully coupled simulation which are then further analyzed in terms of radiative effects, global energy budget and fluctuations of wall heat flux and temperature.     

Nonlinear analysis of a rub-impact rotor supported by turbulent couple stress fluid film journal bearings under quadratic damping

This work reports a numerical study undertaken to investigate the dynamic response of a rotor supported by two turbulent flow model journal bearings with nonlinear suspension and lubricated with couple stress fluid under quadratic damping. This may be the first time that analysis of rotor-bearing system considered the quadratic damping effect. The dynamic response of the rotor center and bearing center are studied. The analysis methods employed in this study are inclusive of the dynamic trajectories of the rotor center and bearing center, power spectra, Poincaré maps and bifurcation diagrams. The maximum Lyapunov exponent analysis is also used to identify the onset of chaotic motion. The modeling results provide some useful insights into the design and development of rotor-bearing system for rotating machinery that operates at highly rotational speed and highly nonlinear regimes.     

Nonlinear ellipsometric method for measuring second-order cascaded phase shift

An ellipsometric method for measuring second-order cascaded phase shift is experimentally demonstrated in a KNbO(3) single crystal. We analyze the polarization state composed of the two orthogonal polarizations of the transmitted fundamental wave, one of which experiences intensity-dependent depletion and phase shift while the other does not. This method does not require a well-defined beam profile or interferometric stability.     

Chemodosimetric Hg2+-selective signaling by mercuration of dichlorofluorescein derivatives

The chemodosimetric behavior of dichlorofluorescein derivatives toward Hg(2+) ions was investigated. Simple chemodosimetric systems showed selective and efficient signaling behaviors toward micromolar concentrations of Hg(2+) ions over other common interfering metal ions in an aqueous environment. The signaling mechanism is selective mercuration of the 4',5'-position of the xanthene moiety, which results in efficient chromogenic and fluorogenic signaling of Hg(2+) ions in aqueous environment.     

Spectroscopic observation of critical guest concentration appearing in tert-butyl alcohol clathrate hydrate

The tert-butyl alcohol (TBA) is the most hydrophobic of the simple alcohol and by itself does not form a clathrate hydrate with water. A genuine clathrate hydrate is synthesized by exposing a gaseous guest to solid TBA + H2O powders. Here, we examine three consecutive spectroscopic approaches of (1) the occurrence of a "free" OH stretching band (nu(OH)) signal of TBA molecules representing an absence of hydrogen bonding between the host water and guest TBA, (2) a tuning effect for creating fresh cages via the rearrangement of the host-water lattice, and finally (3) the existence of a critical guest concentration (CGC) that appears only when the TBA concentration is dilute. The present findings from this simple three-step approach can be extended to other alcoholic guest species with the specific modifications to provide the new insights into inclusion chemistry.     

Preparation and X-ray structures of 3-[Bis(trifluoroacetoxy)iodo]benzoic acid and 3-[hydroxy(tosyloxy)iodo]benzoic acid: new recyclable hypervalent iodine reagents

Preparation, structural characterization, and reactivity of 3-[bis(trifluoroacetoxy)iodo]benzoic acid and 3-[hydroxy(tosyloxy)iodo]benzoic acid, new recyclable iodine(III) reagents derived from 3-iodosylbenzoic acid, are described. The reduced form of these reagents, 3-iodobenzoic acid, can be easily recovered from the reaction mixtures using ion-exchange resin or basic aqueous workup followed by acidification with HCl.     

Structural transformation due to Co-host inclusion in ionic clathrate hydrates

The present findings on the co-host role in restructuring the host water framework might provide important information on tuning the cage dimensions via lattice distortion and promoting the total number of cages via structural transformation. This co-host-induced structural modification can improve the physicochemical properties of ionized clathrate hydrates, particularly given that the host framework is able to function as a pathway to deliver protons or electrons.     

Synthesis of poly(sorbitan methacrylate) hydrogel by free-radical polymerization

Hydrogels are materials with the ability to swell in water through the retention of significant fractions of water within their structures. Owing to their relatively high degree of biocompatibility, hydrogels have been utilized in a host of biomedical applications. In an attempt to determine the optimum conditions for hydrogel synthesis by the free-radical polymerization of sorbitan methacrylate (SMA), the hydrogel used in this study was well polymerized under the following conditions: 50% (w/v) SMA as monomer, 1% (w/w) alpha, alpha'-azo-bis(isobutyro-nitrile) as thermal initiator, and 1% (w/w) ethylene glycol dimethacrylate as cross-liking agent. Under these conditions, the moisture content of the polymerized SMA hydrogel was higher than in the other conditions. Moreover, the moisture content of the poly(SMA) hydrogel was also found to be higher than that of the poly(methyl methacrylate [MMA]) hydrogel. When the Fourier transform-infrared spectrum of poly(SMA) hydrogel was compared with that of poly(MMA) hydrogel, we noted a band at 1735-1730/cm, which did not appear in the Fourier transform-infrared spectrum of poly(MMA). The surface of the poly(SMA) hydrogel was visualized through scanning electron microscopy, and was uniform and clear in appearance.     

Resolution of infrared matrix-assisted laser desorption/ionization time-of-flight mass spectrometry using glycerol; enhancement with a disperse laser beam

Some experimental factors affecting the resolution in glycerol infrared matrix-assisted laser desorption/ionization (IR-MALDI) time-of-flight (TOF) mass spectrometry were investigated. Loading the sample inside a cavity covered with a grid was found to improve the resolving power as reported previously, although not to the extent attainable in UV-MALDI using the same instrument. The resolving power improved as the laser spot area at the sample position got larger, becoming almost comparable with that in UV-MALDI when the spot area was a little larger than the cavity size. Reduced concentration of the ablated materials in the acceleration region with the use of the grid and large irradiation area may be responsible for the enhanced resolution. In addition, the threshold laser fluences measured in this work were lower than those reported in the literature and tended to decrease more rapidly as the irradiation area increased than predicted previously. The implication of similar threshold fluences for matrix and analyte ions is discussed in relation to the analyte ion formation mechanism.