New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Retrospectively gated cardiac cine imaging with temporal and spatial acceleration

Parallel imaging methods are routinely used to accelerate the image acquisition process in cardiac cine imaging. The addition of a temporal acceleration method, whereby k-space is sampled differently for different time frames, has been shown in prior work to improve image quality as compared to parallel imaging by itself. However, such temporal acceleration strategies prove difficult to combine with retrospectively gated cine imaging. The only currently published method to feature such combination, by Hansen et al. [Magn Reson Med 55 (2006) 85-91] tends to be associated with prohibitively long reconstruction times. The goal of the present work was to develop a retrospectively gated cardiac cine method that features both parallel imaging and temporal acceleration, capable of achieving significant acceleration factors on commonly available hardware and associated with reconstruction times short enough for practical use in a clinical context.Seven cardiac patients and a healthy volunteer were recruited and imaged, with acceleration factors of 3.5 or 4.5, using an eight-channel product cardiac array on a 1.5-T system. The prescribed FOV value proved slightly too small in three patients, and one of the patients had a bigemini condition. Despite these additional challenges, good-quality results were obtained for all slices and all patients, with a reconstruction time of 0.98±0.07 s per frame, or about 20 s for a 20-frame slice, using a single processor on a single PC. As compared to using parallel imaging by itself, the addition of a temporal acceleration strategy provided much resistance to artifacts.     

Application of FT-ICR-MS for the study of proton-transfer reactions involving biomolecules

Fourier transform ion cyclotron resonance mass spectrometry, combined with modern ionization (fast atom bombardment , electrospray ionization, matrix-assisted laser desorption–ionization), fragmentation (collision-induced dissociation, surface-induced dissociation, one-photon ultraviolet photodissociation, infrared multiphoton dissociation, blackbody infrared radiative dissociation, electron-capture dissociation), and separation (high-performance liquid chromatography, liquid chromatography, capillary electrophoresis) techniques is now becoming one of the most attractive and frequently used instrumental platforms for gas-phase studies of biomolecules such as amino acids, bioamines, peptides, polypeptides, proteins, nucleobases, nucleosides, nucleotides, polynucleotides, nucleic acids, saccharides, polysaccharides, etc. Since it gives the possibilities to trap the ions from a few seconds up to thousands of seconds, it is often applied to study ion/molecule reactions in the gas phase, particularly proton-transfer reactions which provide important information on acid–base properties. These properties determine in part the three-dimensional structure of biomolecules, most of their intramolecular and intermolecular interactions, and consequently their biological activity. They also indicate the form (unionized, zwitterionic, protonated, or deprotonated) which the biomolecule may take in a nonpolar environment. Figure Biomolecules in the gas-phase acidity-basicity scale     

Enhancing the acquisition efficiency of fast magnetic resonance imaging via broadband encoding of signal content

Current efficient magnetic resonance imaging (MRI) methods such as parallel-imaging and k-t methods encode MR signals using a set of effective encoding functions other than the Fourier basis. This work revisits the proposition of directly manipulating the set of effective encoding functions at the radiofrequency excitation step in order to increase MRI efficiency. This approach, often termed "broadband encoding," enables the application of algebraic matrix factorization technologies to extract efficiency by representing and encoding MR signal content in a compacted form. Broadband imaging equivalents of fast multiecho, parallel and k-t MRI are developed and analyzed. The potential of these techniques to increase the time efficiency of data acquisition is experimentally verified on a commercial MRI scanner using simple spin-echo imaging. A three-dimensional gradient-echo dynamic imaging application that demonstrates the potential benefits of this approach compared to the present state of the art for certain applications is also presented.     

Temperature dependence of the evaporation coefficient of water in air and nitrogen under atmospheric pressure: study in water droplets

The evaporation coefficients of water in air and nitrogen were found as a function of temperature by studying the evaporation of a pure water droplet. The droplet was levitated in an electrodynamic trap placed in a climatic chamber maintaining atmospheric pressure. Droplet radius evolution and evaporation dynamics were studied with high precision by analyzing the angle-resolved light scattering Mie interference patterns. A model of quasi-stationary droplet evolution accounting for the kinetic effects near the droplet surface was applied. In particular, the effect of thermal effusion (a short-range analogue of thermal diffusion) was discussed and accounted for. The evaporation coefficient alpha in air and in nitrogen were found to be equal. The alpha was found to decrease from approximately 0.18 to approximately 0.13 for the temperature range from 273.1 to 293.1 K and follow the trend given by the Arrhenius formula. The agreement with condensation coefficient values obtained with an essentially different method by Li et al. [Li, Y.; Davidovits, P.; Shi, Q.; Jayne, J.; Kolb, C.; Worsnop, D. J. Phys. Chem. A. 2001, 105, 10627] was found to be excellent. The comparison of experimental conditions used in both methods revealed no dependence of the evaporation/condensation coefficient on the droplet charge nor the ambient gas pressure within the experimental parameters range. The average value of the thermal accommodation coefficient over the same temperature range was found to be 1 +/- 0.05.     

Avoparcin, a new macrocyclic antibiotic chiral run buffer additive for capillary electrophoresis.

Avoparcin, like vancomycin, teicoplanin, and ristocetin A, belongs to the family of macrocyclic glycopeptide antibiotics. These antibiotics have all been used as effective chiral selectors for capillary electrophoresis (CE), thin-layer chromatography (TLC), and high performance liquid chromatography (HPLC). The present work focuses on avoparcin, which has been shown to be an excellent chiral selector for the CE enantioseparation of many N-blocked amino acids, as well as several anti-inflammatory drugs of pharmaceutical importance. The use of avoparcin as a chiral run buffer additive in CE is discussed, as well as the effects of changing experimental parameters, like avoparcin concentration, pH, organic modifiers, etc. Comparisons of enantioseparations of some N-3,5-dinitrobenzoyl-derivatized amino acids, using either avoparcin, ristocetin A, teicoplanin, or vancomycin in the run buffer, are also made. In general, vancomycin had the longest migration times, and ristocetin A the shortest, while avoparcin was intermediate. Generally, at least one of the four chiral selectors produced an excellent separation, while a different macrocyclic antibiotic produced a poor separation. Currently, we see no way to predict which chiral run buffer additive will be best or worst for an individual solute.     

Effect of viscous dissipation on the mixed convection heat transfer from an exponentially stretching surface

The mixed convection flow and heat transfer from an exponentially stretching vertical surface in a quiescent fluid is analyzed using similarity solution technique. Wall temperature and stretching velocity are assumed to have specific exponential function forms. The influence of buoyancy along with viscous dissipation on the convective transport in the boundary layer region is analyzed in both aiding and opposing flow situations. The flow is governed by the mixed convection parameter Gr/Re². The velocity and temperature inside the boundary layer are observed to be influenced by the parameters like Prandtl number Pr, Gebhart number Gb. Significant changes are observed in non-dimensional skin friction and heat transfer coefficients due to viscous dissipation in the medium. The flow and temperature distributions inside the boundary layer are analyzed and the results for non-dimensional skin friction and heat transfer coefficients are discussed through computer generated plots.