Intermolecular crosslinking of fatty acyl chains in phospholipids: use of photoactivable carbene precursors.

Abstract:

:Phospholipids containing photolysable carbene precursors (beta-trifluoro-alpha-diazopropionoxy and m-diazirinophenoxy groups) in omega-positions of sn-2 fatty acyl chains were prepared. Photolysis of their vesicles produced crosslinked products in 40-60% yields. Crosslinking was mostly intermolecular and occurred by carbene insertion into the C-H bonds of a second fatty acyl chain. Crosslinking products were characterized by (i) their gel permeation behavior, (ii) analysis of products formed by base-catalyzed transesterification, (iii) degradation with phospholipases A2 and C, (iv) gas chromatography/mass spectrometry, and (v) use of mixtures of phospholipids carrying the carbene precursors and a phospholipid containing radioactively labeled fatty acyl groups. Nitrenes generated from the aliphatic or aromatic azido groups in phospholipids were unsatisfactory for forming crosslinks by insertion in C-H bonds.

authors

Gupta CM,Radhakrishnan R,Gerber GE,Olsen WL,Quay SC,Khorana HG

doi

10.1073/pnas.76.6.2595

subject

Has Abstract

pub_date

1979-06-01 00:00:00

pages

2595-9

issue

6

eissn

0027-8424

issn

1091-6490

journal_volume

76

pub_type

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