Counting the number of solutions in combustion and reactive flow problems

Summary Computational methods and comparison theory enable, when combined, an enhanced capability for counting the number of solutions in combustion equations. Very good lower bounds for the last turning point reveal a stable high temperature explosion branch for very small positive exothermicity.     

Polarization-based balanced heterodyne detection method in a Sagnac interferometer for precision phase measurement

We describe a balanced heterodyne detection method for a Sagnac interferometer that uses a polarization-dependent beam splitter. The signal and the local oscillator are orthogonally polarized components of a single laser beam, permitting the detection of the signal by subtraction of two photocurrents produced in appropriate polarization projections. Using this scheme, we experimentally demonstrate a phase measurement with a sensitivity of 9x10(-10) rad/ radicalHz. The measurement is robust in the presence of laser frequency noise, as a result of preserving the common-path nature of the Sagnac interferometer, and of laser-amplitude noise, as a result of balanced detection.     

On local parton-hadron duality

The multiplicity measure on colour-connected partonic states introduced in [1] is further generalized and we show how to partition the properties of the final state hadronic multiplicity distributions into one part depending upon the partonic cascade and one depending upon the fragmentation inside the Lund model framework. We also show the stability of the measure with respect to variations in the energy and the possible cascade cutoffs and investigate the approximations made in the analytical formulas by means of Monte Carlo simulated events.     

On matrix equivalence and matrix equations

Roth's theorem on the solvability of matrix equations of the form AX?YB=C is proved for matrices with coefficients from a division ring or a ring which is module-finite over its center.     

Externally sensitized mesolytic fragmentations in dithiane-ketone adducts

The apparent activation enthalpies, ΔH^≠, for externally sensitized mesolytic fragmentations in benzophenone-dithiane adducts were obtained in variable temperature photolyses and compared with DFT activation barriers calculated for β-scission in the corresponding oxygen-centered radicals. The results of these experimental and theoretical studies further support the mechanism in which deprotonation of the hydroxy-group, in the transient cation radical, is coupled with intramolecular electron transfer furnishing the O-centered radical, which subsequently fragments. The quantum yields of fragmentation increase for higher alkyl substituted dithiane adducts.     

One-dimensional thin-layer chromatographic separation of phospholipids and lysophospholipids from tissue lipid extracts.

A modified one-dimensional thin-layer chromatographic procedure is presented for the separation from tissues of five phospholipids (phosphatidylserine, phosphatidylethanolamine, phosphatidylinositol, phosphatidylcholine and sphingomyelin) and three lysophospholipids (lysophosphatidylserine, lysophosphatidylethanolamine and lysophosphatidylcholine). This is achieved by simple involvement of 0.4% ammonium sulphate in silica gel H and of acetone in a developing solvent as chloroform-methanol-acetic acid-acetone-water (40:25:7:4:2, v/v). The procedure is simple and the separation is reproducible. The weakness of this method is the partial degradation of phosphatidylethanolamine to lysophosphatidylethanolamine, but a method to prevent this degradation is also presented.     

Chirality determination of unusual amino acids using precolumn derivatization and liquid chromatography-electrospray ionization mass spectrometry

Unusual amino acids such as beta-methoxytyrosine (beta-MeOTyr), allo-threonine (allo-Thr) and allo-isoleucine (allo-Ile) were derivatized with N-alpha-(2,4-dinitro-5-fluorophenyl)-L-alaninamide (FDAA), 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl isothiocyanate (GITC), (S)-N-(4-nitrophenoxycarbonyl)phenylalanine methoxyethyl ester (S-NIFE), or o-phthalaldehyde/isobutyryl-L-cysteine (OPA-IBLC), and then separated via reversed-phase high-performance chromatography followed by UV and electrospray ionization mass spectrometry detection. FDAA generally showed the highest enantioselectivity but the lowest sensitivity among the chiral derivatizing agents (CDAs) investigated. The detection limit of FDAA-derivatized amino acids was in the low picomolar range. Although the enantioselectivity of FDAA derivatives was generally quite high, its selectivity among beta-MeOTyr isomers was poor. The best separation of beta-MeOTyr stereoisomers was achieved with S-NIFE. Due to the complex relationships between the investigated CDAs, stereochemical analyses using a combination of two or more of the CDAs gave the most reliable results for a given separation problem. In general, the methods described are selective and reliable, and are being applied to the analysis of unusual amino acids as they occur in marine peptides.     

Separation of recombinant apolipoprotein A-I(Milano) modified forms and aggregates in an industrial ion-exchange chromatography unit operation

We have shown how protein self-association impacts the ion-exchange separation of modified forms and aggregates for apolipoprotein A-I(Milano). It is well known that reversible self-association of a protein can lead to chromatographic band broadening, peak splitting, merging, fronting, and tailing. To mitigate these effects, urea or an organic modifier can be added to the chromatography buffers to shift the equilibrium distribution of the target molecule to the dissociated form. A first generation process that did not utilize urea resulted in low yield and low purity as it was not possible to separate protein aggregates. A second generation process run in the presence of 6M urea resulted in high purity and high yield, but throughput was limited due to low resin binding capacity when the protein was completely denatured. A third generation process achieved high purity, high yield, and high throughput by shifting the urea concentration during the process to continually operate in the optimal window for maximum loading and selectivity. Key to these systematic process improvements was the rational understanding of the interplay of urea concentration and ion-exchange chromatographic behavior. Results from pilot and industrial scale operations are presented, demonstrating the suitability of the techniques described in this work for the large scale manufacture of recombinant therapeutic proteins.