Cu(II) cross-linked antiparallel dipeptide duplexes using heterofunctional ligand-substituted aminoethylglycine.
Two artificial dipeptides containing both a pendant monodentate (pyridine (py)) and tridentate (terpyridine (tpy) or phenyl terpyridine (varphi-tpy)) ligand on an aminoethylglycine (aeg) backbone have been synthesized. These oligopeptides are fully characterized by one and two-dimensional NMR spectroscopy, mass spectrometry, and elemental analysis. The ligands were chosen because they coordinate Cu(2+) to form [Cu(py)(tpy)](2+) complexes; when bound to the dipeptide scaffold, Cu(2+) chelation cross-links the strands to form double-stranded duplex structures with an antiparallel arrangement. Using spectrophotometric titrations, we observe coordination of one Cu(2+) metal per dipeptide strand. Mass spectrometry, NMR spectroscopy, vapor pressure osmometry, and HPLC confirm that the resulting structures are the dipeptide duplex cross-linked by two metal centers.
Coppock
Matthew B
MB
Department of Chemistry, The Pennsylvania State University, 104 Chemistry Building, University Park, Pennsylvania 16802, USA.
Kapelewski
Matthew T
MT
Youm
Hye Won
HW
Levine
Lauren A
LA
Miller
James R
JR
Myers
Carl P
CP
Williams
Mary Elizabeth
ME
D003300:Copper / Q000737:chemistry*; D004151:Dipeptides / Q000737:chemistry*; D005998:Glycine / Q000031:analogs & derivatives* / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D004151:Dipeptides; D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper; D005998:Glycine