Rapid quantitative measurements of proteomes by Fourier transform ion cyclotron resonance mass spectrometry.

The patterns of gene expression, post-translational modifications, protein/biomolecular interactions, and how these may be affected by changes in the environment, cannot be accurately predicted from DNA sequences. Approaches for proteome characterization are generally based upon mass spectrometric analysis of in-gel digested two dimensional polyacrylamide gel electrophoresis (2-D PAGE) separated proteins, allowing relatively rapid protein identification compared to conventional approaches. This technique, however, is constrained by the speed of the 2-D PAGE separations, the sensitivity limits intrinsic to staining necessary for protein visualization, the speed and sensitivity of subsequent mass spectrometric analyses for identification, and the limited ability for accurate quantitative measurements based on differences in spot intensity. We are presently developing alternative approaches for proteomics based upon the combination of fast capillary electrophoresis, or other suitable chromatographic separations, and the high mass accuracy and sensitivity obtainable with unique Fourier transform ion cyclotron resonance (FTICR) mass spectrometers available at our laboratory. Several approaches are presently being pursued; one based upon the analysis of intact proteins and the second upon approaches for global protein digestion and accurate peptide mass analysis. Quantitation of protein/peptide levels are based on using two or more stable-isotope labeled versions of proteomes which are combined to obtain precise quantitation of relative protein abundances. We describe the status of our efforts towards the development of a high-throughput proteomics capability and present initial results for application to several microorganisms and discuss our efforts for extending the developed capability to mammalian proteomes.     

Some upper bounds of partial sums of a trigonometric series cannot be sharpened via lower bounds

Translated fromMatematicheskie Zametki, Vol. 58, No. 3, pp. 447–451, September, 1995.     

Relationship between Forbush effects and X-ray flares

Statistical analysis of a large amount of data for three solar activity cycles (1975–2005) shows that the magnitude and other characteristics of Forbush effects are related to the intensity and longitude of previous solar flares.     

The effect of oxygen on the Ti(OBu)4—AlR3 catalytic system in the dimerization of ethylene to 1-butene

The effect of O₂ on the Ti(OBu)₄-AlR₃ catalytic system in the dimerization of ethylene to 1-butene is studied. It is shown that O₂ readily interacts with excess AlR₃ and reduces the deactivating capability of trialkylaluminium, converting it into the less reactive AlR₂OR. The optimal conditions of the dimerization reaction in the presence of O₂ are found. An explanation of the effect of O₂ on the catalytic system is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 276–279, February, 1995.     

Quantum chemical studies of azoles

The results of theoretical search for model transition states of the electrophilic substitution reaction in 2H-tetrazole (1) without the preliminary formation of N-protonated azolium salts are presented for two routes that were previously suggested by the authors and thermodynamically investigated: A, the attack of molecule 1 by the nucleophile (HO^–(aq)) to form the anion to which the electrophile H₃O⁺(aq)) is added and B, the attack of molecule 1 by the same electrophile followed by the addition of the same nucleophile to the specifically solvated protonated species formed in the preceding reaction step. The calculations were performed using the DFT/B3LYP/6-31G(d) method and the scanning procedure of the potential energy surface (PES). Both steps of route A turned out to be nearly barrierless, while in route B only its first step is barrierless and the second one is conjugated with passing an activation barrier of ～45 kcal mol^–1 between non-interacting or weakly interacting reactants and electrophilic substitution products. Unlike the specifically solvated protonated species of 1H-tetrazole in an aqueous solution, a similar species of 2H-tetrazole does not form a prereaction complex with the attacking nucleophile (HO^–(aq)) and the five-membered ring is destroyed in fact in the nitrogen-containing reaction product formed after passing the activation barrier. The optimized structure of the transition state differs strongly from the nitrogen-containing structure of the reaction product with the destroyed ring, which was found by scanning of the PES.     

Synthesis of Decaborane by the Reaction of Sodium Undecaborate with Mild Organic Oxidants

New organic oxidants (aldehydes and ketones) allowing efficient synthesis of decaborane in a high yield via intermediate alkali metal salt were found. The sodium undecaborate oxidation process was refined, and new reaction stoichiometry was suggested.     

Flow of a vortical stream in the neighborhood of the critical point

A study was made of the axisymmetric flow of a viscous incompressible fluid in the neighborhood of the critical point of an obstacle when steady-state vortices oriented in the direction of the angular coordinate are introduced into the oncoming flow. A solution is presented of the equation for the transfer of a vortex in the case of an external flow containing a single largesize vortex in the low-frequency part of the spectrum. Using a finite integral Hankel transform, the problem is reduced to the solution of a system of ordinary differential equations. It is shown that a sufficiently large-size vortex can have a considerable effect on the structure of viscous flow near an obstacle.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6, pp. 85–89, November–December, 1970.     

Curing of a network polyimide modified with a linear component

The curing and relaxation processes in polymeric composites based on blends of network and linear polyimides applied onto a filler were studied by dielectric spectroscopy. The sensitivity of dielectric spectroscopy to processes occurring in the course of curing was examined.