Determination of the critical parameters of polymer solutions

The contribution of short-range orientation order to the chemical potentials of components in a polymer-solvent system was determined. The temperature dependence of the degree of orientation of solvent molecules relative to polymer chains in a polyisobutylene-benzene system was obtained. It was shown that the short-range order in the polymer-solvent system fails with temperature to a much lesser extent than in the pure solvent. The expressions for the upper and lower critical solution temperatures with allowance for the contribution of short-range order to the entropy and the free energy of solution, as well as to the chemical potentials of components, were found. It was demonstrated that, in the polymer-solvent system, two upper and two lower critical solution temperatures can exist.     

Redox Economy in Organic Synthesis

Stimulus package for organic synthesis : The economy of step and atom usage has been widely reviewed and acknowledged as being useful frameworks to evaluate the efficiency of synthesis. This Review brings to attention another form of economy which should be considered in the planning and evaluation of a multistep synthesis: redox economy. Several guidelines and examples are included to illustrate the logic of this approach and to stimulate the design of syntheses.

     

Measurement of deamidation of intact proteins by isotopic envelope and mass defect with ion cyclotron resonance Fourier transform mass spectrometry

After synthesis and folding, proteins undergo many post-synthetic modifications, including cleavage, oxidation, glycosylation, methylation, racemization, phosphorylation, and deamidation. Of these modifications, non-enymatic deamidation is the most prevalent. Each asparaginyl and glutaminyl residue in a protein is a miniature molecular clock that deamidates with a genetically determined half-time. These half-times vary from a few hours to more than a century, depending on a primary, secondary, tertiary, and quaternary structure near the amide residue. It has been suggested that these clocks regulate many biological processes. A few such processes have been discovered. These discoveries have been difficult because deamidation is inconvenient to measure. While most post-synthetic changes are easily measured by mass spectrometry, deamidation increases molecular mass by only one nominal Dalton, so the deamidated isotopic envelope overlaps the undeamidated isotopic envelope. While peptide deamidation rate determination through deconvolution of these envelopes has been accomplished for several hundred peptides, deconvolution becomes more difficult as the molecular weight increases. In high-resolution mass spectrometers, this deconvolution is possible for larger molecules and an alternative method based on the 19 mDa mass defect between the deamidated envelope and the isotopic envelope of protein fragments can also be utilized. We herein report a comparison of the envelope deconvolution and the mass defect methods for measurement of deamidation in human eye lens crystallins, with special emphasis on betaB2 crystallin and gammaS crystallin. Measurement of extent of deamidation of betaB2 crystallin in a 7 Tesla ion cyclotron resonance Fourier transform mass spectrometer is found to be accurate to a relative standard deviation in a single measurement of about 4% for each method. The envelope deconvolution method is further illustrated by detection of deamidation in intact gammaS crystallin, a 20 904 Da protein, and discovery of the principal gammaS deamidation site.     

Dynamics of Diels–Alder reactions involving 2-trialkylsilyloxyfurans

Increasing the size of the silyl group on 2-trialkylsilyloxyfurans reduces the rate of Diels–Alder reactions with maleic acid derivatives. While the exo-adduct resulted from the reaction between 2-silyloxyfurans and maleic anhydride, endo-adducts resulted from the reactions with maleate esters. Analysis of transition state structures for the cycloaddition, calculated at the B3LYP/6-31G1 level of theory, revealed significant stretch-mode asynchronicity in the forming bonds, with selectivity arising from steric interactions that affect torsional strain about the shorter of the forming bonds.     

On the cubic convergence of the Paardekooper method

We show a simple way how asymptotic convergence results can be conveyed from a simple Jacobi method to a block Jacobi method. Our pilot methods are the well known symmetric Jacobi method and the Paardekooper method for reducing a skew-symmetric matrix to the real Schur form. We show resemblance in the quadratic and cubic convergence estimates, but also discrepances in the asymptotic assumptions. By numerical tests we confirm that our asymptotic assumptions for the Paardekooper method are most general.     

Determination of hexafluoropropan-2,2-diol in its binary mixtures with water

A visual titration method for the determination of hexafluoropropan-2,2-diol (HFPD) in HFPD-water mixtures is suggested. The procedure involves the titration of the weakly acidic HFPD with sodium methoxide, using dimethylformamide or ethanol as solvent and thymol blue as indicator. The results are in good agreement with the ones obtained by potentiometric titration in water.     

On the global and cubic convergence of a quasi-cyclic Jacobi method

Summary In this paper we consider the global and the cubic convergence of a quasi-cyclic Jacobi method for the symmetric eigenvalue, problem. The method belongs to a class of quasi-cyclic methods recently proposed by W. Mascarenhas. Mascarenhas showed that the methods from his class asymptotically converge cubically per quasi-sweep (one quasi-sweep is equivalent to 1.25 cyclic sweeps) provided the eigenvalues are simple. Here we prove the global convergence of our method and derive very sharp asymptotic convergence bounds in the general case of multiple eigenvalues. We discuss the ultimate cubic convergence of the method and present several numerical examples which all well comply with the theory.This work was supported in part by the University of Minnesota Army High Performance Computing Research Center and the U.S Army Contract DAAL03-89-C-0038. The paper was partly written while this author was a visiting faculty in the Department of Mathematics, University of Kansas, Lawrence, Kansas. The first version of this paper was made in July 1990 while this author was visiting AHPCRC.