Polyporphyrin Thin Films from the Interfacial Polymerization of Mercaptoporphyrins

Abstract

Free-standing ultrathin films of a porphyrin homopolymer have been synthesized by interfacial polymerization of a mercaptoporphyrin. Coupling of 5,10,15,20-tetrakis(α-mercapto-p-tolyl)porphyrin at the water/chloroform interface by copper acetate yields continuous, flexible films after drying with supercritical CO2. These films are amorphous and retain many characteristics of the monomeric porphyrin, such as the property that they may be metalated. Spectroscopic evidence suggests efficient cross-linking of thiols through disulfide coupling occurs in these polyporphyrins to form a network. Polymerization is accompanied by the introduction of carbonyl functionality, probably the transformation of residual thiols to thioacetate by metal-mediated reaction with excess acetate ion. As an example of the catalytic properties of these polymers, they are shown to promote photooxidation of thietane to the corresponding sulfoxide by sensitizing singlet oxygen production.

Design and Photophysical Properties of Zinc(II) Porphyrin‐Containing Dendrons Linked to a Central Artificial Special Pair

“…[7] The bromine atom was subsequently replaced by an azide group by using sodium azide in DMSO. [8] Dipyrromethane 6 was obtained by a classical condensation of aldehyde 5 with excess neat pyrrole, catalyzed by trifluoroacetic acid (TFA; Scheme 3).…”

[5]Rotaxane and [5]Pseudorotaxane Based on Cucurbit[6]uril and Anchored to a Meso-tetraphenyl Porphyrin

“…[5]Rotaxane 4b and [5]pseudorotaxane 4a were synthesized according to Scheme 1. To synthesize the propargylic porphyrin 3, the precursor porphyrin 2 [10] was treated with excess propargylamine to prevent the overalkylation.…”

“…Synthesis of Prop-2-ynyl-{4- [10,15,prop-2-ynylaminomethyl-phenyl)-porphyrin-5-yl]-benzyl}-amine tetrahydrochloride 3…”

Polydopamine as a Catalyst for Thiol Coupling

“…[1][2][3][4][5][6] They playacrucial role in maintaining the conformationals tability and biological activity of proteins [1,2] and participate in the adhesion process of mussel foot protein. [4,5] Over the past decades, these chemicals have received much attentiona saresult of their artificial applicationsi ns ynthesizing pharmaceutical molecules, [7,8] constructing functional materials, [9][10][11] building dynamic combinatorial libraries, [12,13] and preparing sulfur-containing organic compounds. [14,15] Numerous methods have been developed to form disulfide bonds in both scientific laboratories and industrial factories.…”