The acid-catalysed hydrolysis of O-methyl dimethylthiophosphinate. Direct evidence for pentaco-ordinate intermediate formation in the conversion of the PS ester into the PO ester

Author(s):  
Robert D. Cook ◽  
Marlene Metni
1990 ◽  
Vol 10 (3) ◽  
pp. 1134-1144 ◽  
Author(s):  
F Rozen ◽  
I Edery ◽  
K Meerovitch ◽  
T E Dever ◽  
W C Merrick ◽  
...  

The mechanism of ribosome binding to eucaryotic mRNAs is not well understood, but it requires the participation of eucaryotic initiation factors eIF-4A, eIF-4B, and eIF-4F and the hydrolysis of ATP. Evidence has accumulated in support of a model in which these initiation factors function to unwind the 5'-proximal secondary structure in mRNA to facilitate ribosome binding. To obtain direct evidence for initiation factor-mediated RNA unwinding, we developed a simple assay to determine RNA helicase activity, and we show that eIF-4A or eIF-4F, in combination with eIF-4B, exhibits helicase activity. A striking and unprecedented feature of this activity is that it functions in a bidirectional manner. Thus, unwinding can occur either in the 5'-to-3' or 3'-to-5' direction. Unwinding in the 5'-to-3' direction by eIF-4F (the cap-binding protein complex), in conjunction with eIF-4B, was stimulated by the presence of the RNA 5' cap structure, whereas unwinding in the 3'-to-5' direction was completely cap independent. These results are discussed with respect to cap-dependent versus cap-independent mechanisms of ribosome binding to eucaryotic mRNAs.


1933 ◽  
Vol 6 (2) ◽  
pp. 273-277
Author(s):  
Keiichi Shimada

Abstract While there is a difference of opinion as to the exact mechanism involved, it is generally agreed that the action of organic accelerators in hastening the vulcanization process is usually attributed to the conversion of the sulfur into an active form, probably through the intermediate formation of a compound capable of yielding “nascent” sulfur. But some workers, (Ames, J. Soc. Chem. Ind., 43, 117T (1924); Kirchhof, Kolloid-Z.,, 14, 35 (1914); Twiss, J. Soc. Chem. Ind., 35, 782 (1917); Ditmar, Z. angew. Chem., 34, 465 (1921)) have suggested that the action of organic accelerators might be on the rubber hydrocarbon itself. This theory has not been generally developed, though it has received some small amount of evidence through the works of Le Blanc and Kröger (Z. Elektrochem., 27, 335 (1921)) and Naunton (J. Soc. Chem. Ind., 44, 243T (1925)). These investigators found that the viscosity of rubber solutions decreased with the introduction of an organic accelerator, and referred this phenomenon as a “depolymerization” of rubber. These observations possibly suggest that the influence of accelerators is exerted upon the rubber and constitute the only direct evidence in favor of this view.


1965 ◽  
Vol 43 (8) ◽  
pp. 1271-1275 ◽  
Author(s):  
A. Hassan ◽  
S. M. A. D. Zayed

Direct evidence for the hydrolysis of O-methyl ester linkage(s) of Dipterex in the rat has been obtained using Dipterex in which the two methyl groups are C14-labelled. Following a single injection (i.p.) of radio-Dipterex, about 60% of the C14activity was recovered, after 24 hours, in the expired air and in the urine. C14O2and C14-formate constituted about 50% of the recovered radioactivity. The contribution of P—OCH3cleavage to the detoxification of the insecticide has been discussed. A scheme for the fate of the methyl groups has been suggested.


2000 ◽  
Vol 38 (4) ◽  
pp. 301-308 ◽  
Author(s):  
Richard A. Fluck ◽  
Phyllis A. Leber ◽  
John D. Lieser ◽  
Sandra K. Szczerbicki ◽  
Jeffrey G. Varnes ◽  
...  

1990 ◽  
Vol 10 (3) ◽  
pp. 1134-1144 ◽  
Author(s):  
F Rozen ◽  
I Edery ◽  
K Meerovitch ◽  
T E Dever ◽  
W C Merrick ◽  
...  

The mechanism of ribosome binding to eucaryotic mRNAs is not well understood, but it requires the participation of eucaryotic initiation factors eIF-4A, eIF-4B, and eIF-4F and the hydrolysis of ATP. Evidence has accumulated in support of a model in which these initiation factors function to unwind the 5'-proximal secondary structure in mRNA to facilitate ribosome binding. To obtain direct evidence for initiation factor-mediated RNA unwinding, we developed a simple assay to determine RNA helicase activity, and we show that eIF-4A or eIF-4F, in combination with eIF-4B, exhibits helicase activity. A striking and unprecedented feature of this activity is that it functions in a bidirectional manner. Thus, unwinding can occur either in the 5'-to-3' or 3'-to-5' direction. Unwinding in the 5'-to-3' direction by eIF-4F (the cap-binding protein complex), in conjunction with eIF-4B, was stimulated by the presence of the RNA 5' cap structure, whereas unwinding in the 3'-to-5' direction was completely cap independent. These results are discussed with respect to cap-dependent versus cap-independent mechanisms of ribosome binding to eucaryotic mRNAs.


1962 ◽  
Vol 40 (6) ◽  
pp. 1196-1200 ◽  
Author(s):  
G. G. S. Dutton ◽  
A. M. Unrau

Only D-glucose was obtained on acid hydrolysis of the glucan. Periodate oxidation released formaldehyde, which was believed to arise from C6 of D-glucofuranose units. From the additional formaldehyde liberated from the borohydride-reduced glucan the degree of polymerization was estimated to be about 165. Complete hydrolysis of the derived polyalcohol gave glycerol, erythritol, D-glucose, and D-xylose. Partial hydrolysis gave glycerol, erythritol, and at least seven non-reducing oligosaccharides. Direct evidence for the existence of relatively large numbers of 1 → 6 and 1 → 4 linkages was found, together with smaller numbers of 1 → 2 linkages. The methylated glucan was freely soluble in chloroform – petroleum ether (5:95), and hydrolysis gave tetra, tri, di, and mono-O-methyl-D-glucoses in a 6:6:3:1 molar ratio.


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