Phenanthroline, copper

Although the number of applications of olefin metathesis to transition metal complexes is small compared to the number of applications in organic synthesis, this field is becoming increasingly important. Spectacular examples are the double RCM reactions of copper phenanthroline complexes as a synthetic route to catenanes [113] or a recently reported approach to steric shielding of rhenium complex terminated sp-carbon chains [114]. 

Further interesting redox modified polypyrrole films were prepared e.g. a polymeric copper phenanthroline complex that can be reversibly de- and re-metallated because it retains the pseudotetrahedral environment after decomple-xation, A very diversified electrochemistry is displayed by polypyrrole films containing electron donor as well as electron acceptor redox centers in the same film... 

Winyard, P.G., Pall, H., Lunec, J. and Blake, D.R. (1987b). Non-caeruloplasmin-bound copper ( phenanthroline copper ) is not detectable in fresh serum or synovial fluid from patients with rheumatoid arthritis. Biochem. J. 247, 245-247. 

Chen T, Greenberg MM (1998) Model studies indicate that copper phenanthroline induces direct strand breaks via (5-elimination of the 2 -deoxyribonolactone intermediate observed in ene-diyne mediated DNA damage. J Am Chem Soc 120 3815-3816 Chen T, Cook GP, Koppisch AT, Greenberg MM (2000) Investigation of the origin of the sequence selectivity for the 5-halo-2 -deoxyuridine sensitization of DNA to damage by UV-irradiation. J Am Chem Soc 122 3861-3866... 

Cunningham CT, Cunningham KLH, Michalec JF, McMillin DR. Cooperative substituent effects on the excited states of copper phenanthrolines. Inorg Chem 1999 38 4388-92. 

Recent studies with copper phenanthroline complexes expand on the possibilities for site-directed oxidation-reduction chemistry of copper complexes. Cu(ii)(l,10-phenanthroline)2, alone or tethered to various DNA-binding domains, causes DNA strand scission in vitro in the presence of reductants, which involves the formation of the hydroxyl radical or its equivalent." - Upon reaction of Cu(ii)(Phen)2 with tumor cells, it is likely that the complex binds directly to DNA, acting as a site-directed catalyst for the generation of oxyradi-cals. ... 

Complexes of metal + ligand + protein or DNA can also catalyze the Diels Alder cycloaddition or oxidations with hydrogen peroxide. Copper complexes bound to DNA catalyzed the Diels-Alder cycloaddition with up to 99% ee [15, 16], Cu(phthalocyanine) complexed to serum albumin also catalyzed the enantioselective (98% ee) Diels-Alder reaction, but only with very high catalyst loading (10 mol%) and only with pyridine-bearing dienophiles (presumably to complex the copper) [17]. Achiral Cr(III) complexes or Mn(Schiff-base) complexes inserted into the active site of apomyoglobin variants catalyzed the sulfoxidation of thio-anisole with up to 13 and 51% ee, respectively [18, 19]. A copper phenanthroline complex attached to the adipocyte lipid-binding protein catalyzed the enantioselective hydrolysis of esters and amides [20]. 

The nuclease activity of the copper-phenanthroline complex has been also directed at specific sites by conjugation to DNA-binding proteins (trp (72), CAP (75), Cro (74), Pis (75), NarL (76)) in order to study the interactions of these DNA-binding proteins with their DNA targets or to isolate long DNA... 

Intramolecular association between C o and zinc porphyrins are rather common events in multi component systems containing these chromo-phores [95], however, none of these interlocked structures are reported to display such a tendency, in spite of the rather flexible polyether chain connecting the donor and the acceptor to the central copper phenanthroline, which could easily allow a close approach of the terminal units. 

Bales BC, Pitie M, Meunier B, Greenberg MM. A minor groove binding copper-phenanthroline conjugate produces direct strand breaks via 3-ehmination of 2-deoxyribonolactone. Jzlm Chem Soc. 2002 124 9062-9063. 

Chen T, Greenberg MM. Model studies indicate that copper phenanthroline induces direct strand breaks via 3-elimination of the 2 -deoxyribonolactone intermediate observed in enediyne mediated DNA damage. Chem Soc. 1998 120 3815-3816. 

Pitie M, Van Horn JD, Brion D, Burrows CJ, Meunier B. Targeting the DNA cleavage activity of copper phenanthroline and Chp-Phen to A T tracts via linkage to a poly-M-methylpyrrole. Bioconjugate Chem. 2000 11 892-900. 

Copper phenanthroline complexes catalyze the oxidation of methanol... 

Lei YB, Anson FC (1994) Mechanistic aspects of the electroreduction of as catalyzed by copper-phenanthroline complexes adsorbed on graphite-electrodes. Inorg Chem 33(22) 5003-5009... 

Using a copper phenanthroline complex as a core, Armaroli et al. synthesized a dendritic compound with fullerene-functionalized branches. Electrochemical... 

To make a knot is a task easily accomplished by a child playing with a rope, or even by a careless adult with shoelaces. For a chemist playing with molecules this is an intrinsically difficult problem and so far only a few of these topologically interesting compounds have been synthesized. A strategy that finally led to success is based on the self-assembly of double-helical copper phenanthroline complexes. The helix represents the core structure from which the trefoil knot 30 in Fig. 15 is obtained in a final cyclization step. It is important to note that a trefoil knot is chiral. The resolution of the two enantiomers was recently accomplished by fractional crystallization of the diastereoisomers obtained with a chiral counterion. 

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