Synthesis of redox derivatives of lysine and related peptides containing phenothiazine or tris(2,2′‐bipyridine)ruthenium(II)

Abstract

Boc‐l‐Lysine derivatives and lysine‐containing peptides bearing the electron donor 10H‐phenothiazine (PTZ) or the redox chromophore tris(2,2′‐bipyridine)ruthenium(II) dication ([Rub3,]2H, where b is 2,2‐bipyridine) have been synthesized and characterized. SeO2 oxidation (53% yield) of 4,4′‐dimethyl‐2,2′‐bipyridine, Ag2:O oxidation (85% yield) of the monoaldehyde, complexation (96% yield) of 4′‐methyl‐2,2′‐bipyridine‐4‐carboxylic acid (m‐OH) with Rub2Cl2:. activation (81% yield) of the acid [Rub2m‐OH]2+ (PF6−)2, and condensation (83% yield) of the succinimido ester [Rub2m‐OSu]2+ (PF6−)2 with Boc‐Lys furnished the protected redox‐chromophore module [Boc‐Lys(Rub2m)‐OH]2+(PF6−)2 in 29% overall yield over five steps. The first two steps constitute the first practical synthesis of the monocarboxylic acid m‐OH (45% overall yield). Also prepared were m‐OSu, Boc‐Lys(m)‐OH, Boc‐Lys(m)‐OCH3, and [Rub2m‐NHCH3]2+ (PF6−)2:. Activation (91% yield) of 3‐(10H‐phenothiazine‐10)propanoic acid (PTZpn‐OH) and condensation (92% yield) of the succinimido ester PTZpn‐OSu with Boc‐Lys furnished the protected electron‐donor module Boc‐Lys(PTZpn)‐OH (84% overall yield). The latter was used in solid‐phase syntheses of two redox tripeptides. CH3CO‐Ala‐Lys(PTZpn)‐Ala‐OH and [Rub2m‐Ala‐Lys(PTZpn)‐Ala‐OH]2 (PF6−)2. The electrochemical properties of these redox amino acids and peptides were similar to those of PTZpn‐OH, [Rub2 m‐OH]2+(PF6)2. or [Rub2 m‐NHCH3]2+ (PF6−)2. Lys(PTZpn). [Lys(Rub2m)]2+ (PF6)2:. and other redox modules may be useful for engineering light‐harvesting proteins, photovoltaic cells, and other molecular electronic devices.

Self‐Beating Artificial Cells: Design of Cross‐Linked Polymersomes Showing Self‐Oscillating Motion

“…Bis (2,2′-bipyridine)(1-(4′-methyl-2,2′-bipyridine-4-carbonyloxy)-2,5-pyrrolidinedione) ruthenium(II) bis (hexafl uorophosphate) (NHSRu(bpy) 3 ) was synthesized according to the previously reported method. [ 43 ] The chain transfer agent, S -1-dodecyl-S ′-( α , α ′-dimethyl-α ″-acetic acid)-trithiocarbonate (purity >99%), was purchased from Trylead Chemical Technology (China) and used as received. The photo-initiator, 2,2′-azobis(2-methylpropionamidine)dihydrochloride, and all other materials were purchased from Wako Pure Chemical Industries (Japan) and used as received.…”

Electronic Properties and Structure of Assemblies of CdSe Nanocrystal Quantum Dots and Ru‐Polypyridine Complexes Probed by Steady State and Time‐Resolved Photoluminescence

“…[ 57 ] The complex [Ru(tpby) 2 (bcb)](PF 6 ) 2 ( 2 ), (tbpy = 4, 4 ′ -di-tert-butyl, 2,2 ′ -bipyridine; bcb = 4, 4 ′ -dicarboxy, 2,2 ′ -bipyridine) was prepared by methods described previously. [ 58 ] Three sizes of CdSe NCs (1S peak at 501 nm, 545 nm, and 593 nm) were prepared by a slightly modifi ed literature procedure. [ 59 ] Prior to the synthesis, TOP was heated and stirred at 200 ° C for 2 h under Ar, and then transferred to the glovebox.…”

Synthesis, Spectroscopic Properties and Electrochemical Oxidation of RuII‐Polypyridyl Complexes Attached to a Peptide Nucleic Acid Monomer Backbone

“…The known compound, [Ru(bpy) 2 (bpy-COOH)] 2+ (1), [37] was chosen as the key synthon for the synthesis of two Ru II -incorporated PNA monomers, M1…”