Reactions between model compounds were carried out at high
temperatures (150−250 °C)
in order to provide a correct simulation of the behavior of hydroxyl
and carboxyl polyester chain ends in
the presence of triphenyl phosphite (TPP). The reaction between
TPP and alcohol (3-phenyl-1-propanol)
leads to phenoxy/alkoxy substitutions on the phosphite. The
elimination of phenol in open systems is
considered as the driving force of this reaction. The occurrence
of multisubstitutions between alcohol
and phosphite is confirmed. On the other hand, carboxylic acid
(4-tert-butylbenzoic acid) reacts with
triphosphite to produce ester (or phenyl ester) and phosphonate.
The driving force is the creation of a
stable phosphoryl bond. NMR experiments lead furthermore to
conclusive results concerning the higher
velocity of the acid reaction with aliphatic phosphite than of the acid
reaction with aromatic phosphite.
In the reactions involving alcohol, acid, and phosphite, the
conditions favoring ester formation are
explained: The presence of TPP is seen to greatly promote the ester
production.
We report the sequencing of a 22,470 bp DNA fragment from the left arm of Saccharomyces cerevisiae chromosome II. Thirteen open reading frames longer than 300 bp provisionally called YBL0520, YBL0401 to YBL0408 and YBL0410 to YBL0413 have been detected. Five genes were previously sequenced: COR1, encoding a core protein of the mitochondrial coenzyme QH2 cytochrome c reductase complex (Tzagaloff and Crivellone, 1986), PRS3, a proteasome subunit gene (Lee et al., 1992), ERD2, coding for a protein involved in the secretory pathway (Semeza et al., 1990), URA7, which encodes a CTP synthetase (Ozier-Kalogeropoulos et al., 1991) and the gene for the ribosomal protein L16 (Pan et al., 1993). Among the others, YBL0406 shows striking homologies to FUR4 (Jund et al., 1988) and DAL4 (Yoo et al., 1992), the uracyl and allantoin permeases; YBL0520 is a DNA-related protein, possibly involved in gene regulation; YBL0412 shares homologies with the mouse alpha-adaptins A and C; and YBL0413 is homologous to a protein of Pseudomonas aeruginosa that is likely to be involved in proline biosynthesis. YBL0401, internal to YBL0520, is probably not expressed.
This report presents the results from IUPAC Working Party IV.2.2 of the global trial within the framework of IUPAC Commission IV.2, “Characterization of Commercial Polymers”. The results were compared on the basis of molecular weight obtained by size exclusion chromatography (SEC)using different techniques practiced in participating laboratories, the majority of which were materials suppliers. The practical methodologies used different solvents for the polymers, in particular, benzyl alcohol, 1,1,1,3,3,3 hexafluoropropan-2-ol and tetrahydrofuran; the latter solvent was used after chemical modification of the polyamides, in general with trifluoroacetic anhydride. Eight laboratories participated in the trial. The repeatability for molecular weight in each laboratory was good, whatever technique was used, the relative standard deviation averaged over all laboratories being around 3%. The deviations in distribution of molecular weights with different experimental methodologies were broader, but were reasonably good despite the diversity of methods. The differences in the distribution correspond to a confidence interval of about 30% in molecular weight.
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