Experimental Van Deemter plots of shear-driven liquid chromatographic separations in disposable microchannels

We present a new stationary phase coating method, yielding a monolayer of densely arrayed porous HPLC beads (d(p)=4 microm) for use in a disposable shear-driven flow LC system. The system is inherently suited for whole-column detection through the small voids between the individual particles of the layer. The chromatographic performance of the system has been characterized by performing a series of coumarin dye separation experiments (reversed-phase mode) and by measuring the theoretical plate height as a function of the mobile phase velocity. The resulting Van Deemter curve, yielding a value of about 90,000 plates/m near the u=u(opt) velocity, shows good agreement with the theoretical expectations, and hence constitutes the first full validation of the theory of shear-driven chromatography.     

Elution mode of Pneumocystis carinii cysts in gravitational field-flow fractionation.

The simplest field-flow fractionation technique, i.e. gravitational, was used in an attempt to purify a Pneumocystis carinii cyst suspension. This parasite is an opportunistic invader in immunocompromised patients, especially those suffering from AIDS. The cyst stage is spherical and 5 microns in diameter. Unexpected retention times, not systematically related to the size and the density of the parasite, were obtained under various experimental conditions. When silicone-coated walls were used, Pneumocystis carinii cysts were eluted in the void volume, whereas when uncoated walls were used with a sodium dodecyl sulphate-enriched carrier phase, retention was observed. These phenomena are probably related to the high degree of hydrophobicity of these micrometre-sized biological particles; this degree can be easily determined. The use of the gravitational field-flow fractionation technique can be of a great interest for the development of new methods for diagnostic purposes. Particle-wall interactions and their modifications due to the carrier phase or to the wall treatment can be employed in the search for new bronchoalveolar lavage solutions.     

Adsorption of liquid-phase alkane mixtures in silicalite: simulations and experiment

A combination of experimental and computational studies of adsorption from liquid-phase mixtures of linear alkanes in the zeolite silicalite is presented here. Configurational biased grand canonical Monte Carlo simulations combined with identity-swap moves are used to equilibrate the simulations in reasonable times. Interesting trends observed in experiments have been captured quantitatively by simulations. A siting analysis of the simulation data reveals that, during adsorption from a liquid mixture, shorter alkanes prefer the zigzag channels and longer alkanes concentrate in the straight channels of silicalite.     

Polyfunctional tetrahydropyrido[2,3-b]pyrazine scaffolds from 4-phenylsulfonyl tetrafluoropyridine

[Reaction: see text]. Polyfunctional tetrahydropyrido[2,3-b]pyrazine scaffolds can be synthesized by sequential reaction of pentafluoropyridine with sodium phenylsulfinate and an appropriate diamine. The polyfunctionality possessed by the difluorinated tetrahydropyrido[2,3-b]pyrazine scaffolds was demonstrated in selected model reactions with nucleophiles to give access to various polysubstituted [6,6]-ring fused systems.     

SPECTROSCOPIC STUDIES ON A RETINYLIDENE-IMINE-TETRAFLUOROBORATE

Abstract— N -retinylidene-butyl-l-aminium tetrafluoroborate (NRBH+BF₄^-) was used to determine the frequencies of the free (non-hydrogen-bonded) v (N+-H) and v (C=NH+) vibrations and their anharmon-icity constants. For this purpose the Fourier-transform IR and near-IR (overtone) spectra were recorded. The visible-UV spectra were also taken. The results locate the free v (N+-H) band at about 3250 ± 50 cm^-1; the vibration has normal anharmonicity while v (C=NH+) is very nearly harmonic. The UV and IR spectra show that the Schiff base is protonated, but that the proton is only very weakly hydrogen-bonded to the anion. Therefore, in this respect, NRBH+BF₄^- is a good model for the hydrogen-bonding environment of the region around the nitrogen of rhodopsin chromophores.     

Etude spectroscopique de derives mercuriques d'amides-thiols: Partie III. Spectres de vibration et structure de complexes mercuriques des thiol-2N-méthylacétamide,thiol-3N-méthylpropanamide et N-thiol-2 éthyle)acétamide

Raman and IR spectra of (CH₃NHCOCH₂S)₂Hg, (CH₃CONHCH₂CH₂S)₂Hg and CH₃NHCOCH₂CH₂SHgCl have been recorded between 3800 and 60 cm^?1. Mercury is covalently bonded to two sulphur atoms in the first two compounds and to one sulphur atom and one chlorine atom in the third compound. (CH₃NHCOCH₂S)₂Hg forms a tenatom ring by intramolecular hydrogen bonding NH?OC. In the two other complexes, weak interactions Hg?O are consistent with experimental results.     

Rate constants from the reaction path Hamiltonian. II. Nonseparable semiclassical transition state theory

For proton transfer reactions, the tunneling contributions to the rates are often much larger than thermally activated rates at temperatures of interest. A number of separable tunneling corrections have been proposed that capture the dependence of tunneling rates on barrier height and imaginary frequency size. However, the effects of reaction pathway curvature and barrier anharmonicity are more difficult to quantify. The nonseparable semiclassical transition state theory (TST) of Hernandez and Miller [Chem. Phys. Lett. 214, 129 (1993)] accounts for curvature and barrier anharmonicity, but it requires prohibitively expensive cubic and quartic derivatives of the potential energy surface at the transition state. This paper shows how the reaction path Hamiltonian can be used to approximate the cubic and quartic derivatives used in nonseparable semiclassical transition state theory. This enables tunneling corrections that include curvature and barrier anharmonicity effects with just three frequency calculations as required by a conventional harmonic transition state theory calculation. The tunneling correction developed here is nonseparable, but can be expressed as a thermal average to enable efficient Monte Carlo calculations. For the proton exchange reaction NH2 + CH4 <==> NH3 + CH3, the nonseparable rates are very accurate at temperatures from 300 K up to about 1000 K where the TST rate itself begins to diverge from the experimental results.     

Analysis of the kinetic mechanism of recombinant human isoprenylcysteine carboxylmethyltransferase (Icmt)

Background  

Isoprenylcysteine carboxyl methyltransferase (Icmt) is the third of three enzymes that posttranslationally modify proteins that contain C-terminal CaaX motifs. The processing of CaaX proteins through this so-called prenylation pathway via a route initiated by addition of an isoprenoid lipid is required for both membrane targeting and function of the proteins. The involvement of many CaaX proteins such as Ras GTPases in oncogenesis and other aberrant proliferative disorders has led to the targeting of the enzymes involved in their processing for therapeutic development, necessitating a detailed understanding of the mechanisms of the enzymes.     

Astaxanthinogenesis in the yeastPhaffia rhodozyma

Astaxanthin is a diketo-dihydroxy-carotenoid produced byPhaffia rhodozyma, a basidiomicetous yeast. A low-cost fermentation medium consisting of raw sugarcane juice and urea was developed to exploit the active sucrolytic/urelolytic enzyme apparatus inherent to the yeast. As compared to the beneficial effect of 0.1 g% urea, a ready nitrogen source, mild phosphoric pre inversion of juice sucrose to glucose and fructose, promptly fermentable carbon sources, resulted in smaller benefits. Corn steep liquor (CSL) was found to be a valuable supplement for both yeast biomass yield (9.2 g dry cells/L) and astaxanthin production (1.3 mg/g cells). Distillery effluent (vinace), despite only a slightly positive effect on yeast growth, allowed for the highest pigment productivity (1.9 mg/g cells). Trace amounts of Ni² (1 mg/L, as a cofactor for urease) resulted in controversial effects, namely, biomass decrease and astaxanthin increase, with no effect on the release (and uptake) of ammonium ion from urea. Since the synthesized astaxanthin is associated with the yeast cell and the pigment requires facilitated release for aquaculture uses (farmed fish meat staining), an investigation of the yeast cell wall was undertaken using detergent-treated cells. The composition of the rigid yeast envelope was found to be heterogeneous. Its partial acid or enzymatic depolymerization revealed glucose and xylose as common monomeric units of the cell-wall glycopolymers. Yeast cell-wall partial depolymerization with appropriate hydrolases may improve the pigment bioavailability for captive aquatic species and poultry.

     

Comprehensive DFT study of nitrous oxide decomposition over Fe-ZSM-5

The reaction mechanism for nitrous oxide decomposition has been studied on hydrated and dehydrated mononuclear iron sites in Fe-ZSM-5 using density functional theory. In total, 46 different surface species with different spin states (spin multiplicity M(S) = 4 or 6) and 63 elementary reactions were considered. Heats of adsorption, activation barriers, reaction rates, and minimum energy pathways were determined. The approximate minimum energy pathways and transition states were calculated using the "growing string method" and a modified "dimer method". Spin surface crossing (e.g., O(2) desorption) was considered. The minimum potential energy structure on the seam of two potential energy surfaces was determined with a multiplier penalty function algorithm by Powell and approximate rates of spin surface crossings were calculated. It was found that nitrous oxide decomposition is first order with respect to nitrous oxide concentration and zero order with respect to oxygen concentration. Water impurities in the gas stream have a strong inhibiting effect. In the concentration range of 1-100 ppb, the presence of water vapor influences the surface composition and the apparent rate coefficient. This is especially relevant in the temperature range of 600-700 K where most experimental kinetic studies are performed. Apparent activation barriers determined over this temperature range vary from 28.4 (1 ppb H(2)O) to 54.8 kcal/mol (100 ppb H(2)O). These results give an explanation why different research groups and different catalyst pretreatments often result in very different activation barriers and preexponential factors. Altogether perfect agreement with experimental results could be achieved.