Synthesis of polymerizable and amphiphilic (porphinato)irons and their copolymers with polymerizable phospholipid

Abstract

This paper describes the synthesis of polymerizable and amphiphilic porphyrins, 5,10,15,20tetrakis[a,a,a,a-o-(ra-[((4"-carboxybutadienyl)carbonyl)oxy]-2',2'-dimethylalkanamido)phenyl]porphyrin (1) and 5,10,15,20-tetrakis[a,a,a,a-o-(n-[((2"-carboxypropenyl)carbonyl)oxy]-2',2'-dimethylalkanamido)phenyl]porphyrin (2), and their copolymers with l,2-bis(2',4'-octadecadienoyl)-sn-glycero-3-phosphocholine. 1, 2, and their (porphinato)iron derivatives have high compatibility with phospholipids and are efficiently copolymerized with the polymerizable phospholipid in a liposome state to give polymerized liposomes covalently containing the porphyrin residues. The oxygen-binding property of the copolymerized (porphinato) iron liposome is also described in comparison with that of a red blood cell.

Supramolecular Assemblies from Amphiphilic Homopolymers: Testing the Scope

“…We hypothesized that incorporating two hydrophilic head groups on either side of an alkyl chain should be able to afford vesicle structures. Polymer vesicles based on amphiphilic polymers have been previously achieved using block copolymers or polymers containing two hydrophobic tails for every hydrophilic head group . In our case, we ask whether polymerized bolamphiphiles are capable of providing vesicle-type assemblies.…”

Polymerizable phospholipids: a novel class of biomaterials

“…The dienoate chromophore absorbs strongly at -257 nm due to conjugated carbonyl group. Therefore, photopolymerization is achieved by exposing vesicle dispersion to 254 nm UV light, at 50 "C for 1-2 hr [55-571 and the course of the polymerization has been monitored either by observing a disappearance of the diene peak in 255-260 nm range [23, 39, 55-58, 61, 70-721, [58,64,67]. The presence of an oligomer or polymer as opposed to a dimer has been demonstrated by the insolubility of freeze-dried vesicles in methylene chloride [72].…”

Highly Stable Polymerizable Vesicles in Anionic Surfactant/Ammonium Salt Mixtures in the Presence of Cross-linking Monomers for Convenient Preparation of Hollow Nanospheres

“…Polymerization reactions in spherically closed amphiphilic bilayers, − i.e., vesicles and liposomes, − are known to fix the vesicular structure to provide stabilized hollow colloidal nanoparticles. − A number of unsaturated phospholipids have been synthesized for stabilization of liposomes. , Polymerization of metastable vesicles, typically formed by the dispersion of bilayer phases of double-chained surfactants incorporating polymerizable groups, lock even the nonequilibrium vesicular structures into place, preventing them from reverting to more stable flat bilayers . A number of amphiphilic cross-linking monomers have been explored to circumvent the problem of intravesicular phase separation that could induce significant deformation of vesicles upon polymerization. − Divinylbenzene (DVB) is known to swell the vesicle bilayers of various double-chained surfactants to act as a simple cross-linking agent. , Polymerization of unilamellar vesicles, spontaneously formed by the mixing of single-chained cationic and anionic surfactants incorporating polymerizable groups, has also been reported .…”

“…Polymerization reactions in spherically closed amphiphilic bilayers, [1][2][3] i.e., vesicles and liposomes, [4][5][6][7][8][9] are known to fix the vesicular structure to provide stabilized hollow colloidal nanoparticles. [10][11][12][13] A number of unsaturated phospholipids have been synthesized for stabilization of liposomes.…”