108. Alkyl–oxygen fission in carboxylic esters. Part I. Esters of αγ-dimethylallyl alcohol and other substituted allyl alcohols

Balfe, Michael P.; Hills, Henry W. J.; Kenyon, Joseph; Phillips, Henry; Platt, Bertie C.

doi:10.1039/jr9420000556

Cited by 2 publications

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“…V UI be highly susceptible to unimolecular and/or bimolecular (i.e. nucleophilically assisted (alkyl-oxygen cleavage to provide formate ion and a 2-substituted Cl8 fragment (Balfe et al, 1942(Balfe et al, , 1951. The nucleophile would presumably be supplied by the protein.…”

Section: Discussionmentioning

confidence: 99%

“…Allylic formates undergo rapid substitution by both unimolecular and bimolecular pathways leading to alkyl-oxygen cleavage (Balfe et al, 1942(Balfe et al, , 1951Kenyon el al., 1936). If a nucleophile such as the carboxylate of Asp-212 were available to attack C13 of retinal in the native membrane to catalyze dark cisfrum isomerization, that nucleophile might attack the analog if it is present at the binding site, at the…”

Section: Introductionmentioning

confidence: 99%

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A Highly Reactive Heteroatom Analog of Retinal and Its Interaction With Bacteriorhodopsin

Birnbaum

Seltzer

1984

Photochem & Photobiology

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Abstract<,,formate ester (5) [2-(6-methyl-8-(2,h,6-trimethyl-l-cyclohexen-l-yl)-3E,5E,7E-octatrienyl formate], a highly reactive analog of retinal, was synthesized and its interaction with bacterioopsin studied. The formate ester, in the absence of purple or bleached membrane, undergoes very rapid reaction (t,,z = 0.9 min) in neutral buffer but with membrane present it diffuses more rapidly into the membrane where it reacts slowly. Incorporation of 5 in the membrane results in a 38 nm (3900 cm-I) red shift which remains after reconstitution with retinal. Similar experiments with the corresponding C,, alcohol (4) results in a red shift, but this absorption blue shifts upon reconstitution with retinal. Washing the formate ester-treated membrane with bovine serum albumin or the corresponding lyophilized preparation with hexane, treatments that remove retinal oxime, fails to remove the UV-visible absorption, suggesting that a covalent bond between the C,, moiety and a nucleophilic group of the protein has probably formed.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Highly Reactive Heteroatom Analog of Retinal and Its Interaction With Bacteriorhodopsin

Birnbaum

Seltzer

1984

Photochem & Photobiology

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A Highly Reactive Heteroatom Analog of Retinal and Its Interaction With Bacteriorhodopsin

Birnbaum

Seltzer

1992

Photochem & Photobiology

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Abstract— C18 formate ester (5) [2‐(6‐methyl‐8‐(2,6,6‐trimethyl‐1‐cyclohexen‐1‐yl)‐3E,5E,7E‐octatrienyl formate], a highly reactive analog of retinal, was synthesized and its interaction with bacterioopsin studied. The formate ester, in the absence of purple or bleached membrane, undergoes very rapid reaction (tl/2= 0.9 min) in neutral buffer but with membrane present it diffuses more rapidly into the membrane where it reacts slowly. Incorporation of 5 in the membrane results in a 38 nm (3900 cm‐1) red shift which remains after reconstitution with retinal. Similar experiments with the corresponding C18 alcohol (4) results in a red shift, but this absorption blue shifts upon reconstitution with retinal. Washing the formate ester‐treated membrane with bovine serum albumin or the corresponding lyophilized preparation with hexane, treatments that remove retinal oxime, fails to remove the UV‐visible absorption, suggesting that a covalent bond between the C18 moiety and a nucleophilic group of the protein has probably formed.

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108. Alkyl–oxygen fission in carboxylic esters. Part I. Esters of αγ-dimethylallyl alcohol and other substituted allyl alcohols

Cited by 2 publications

References 0 publications

A Highly Reactive Heteroatom Analog of Retinal and Its Interaction With Bacteriorhodopsin

A Highly Reactive Heteroatom Analog of Retinal and Its Interaction With Bacteriorhodopsin

A Highly Reactive Heteroatom Analog of Retinal and Its Interaction With Bacteriorhodopsin

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