Distance dependence of intrahelix Ru(II)* to Os(II) polypyridyl excited-state energy transfer in oligoproline assemblies.

Energy transfer between the metal-to-ligand charge transfer (MLCT) excited states of [Pra [M(II)(bpy)2(4-Me-4'(-N(H)CO)bpy)](PF6)2 units ([Pra(M(II)bpy2(mbpy)](2+): M(II) = Ru(II) or Os(II), bpy = 2,2'-bipyridine, mbpy = 4'-methyl-2,2'-bipyridine-4-carboxamido, Pra = 4-M(II)-L-proline) linked covalently to oligoproline assemblies in room temperature acetonitrile occurs on the picosecond-nanosecond time scale and has been time-resolved by transient emission measurements. Three derivatized oligoprolines, [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-2, Pro = L-proline and Glu = glutamic acid); [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-3); and CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)Pro6-Glu2-NH2](6+) (ORR-5), were prepared by using solid-phase peptide synthesis. Given the helical nature of the resulting assemblies and the nature of the synthesis, composition, length, and loading pattern are precisely controlled in the assemblies.

Sensitization of TiO(2) by Phosphonate-Derivatized Proline Assemblies.

Surface electrochemical and photoelectrochemical measurements on ITO (In(2)O(3):Sn) or TiO(2) of two proline assemblies are reported. Surface coverage on ITO of Pbp-pra(Ru(II)b(2)m)-OH(PF(6))(2) and Bpb-pra(Ru(II)b(2)m)-OCH(3)(CF(3)CO(2))(2) are (1.5-2.

Assessment of stereoselectivity of trimethylphenylalanine analogues of delta-opioid [D-Pen(2),D-Pen(5)]-enkephalin.

[D-Pen(2),D-Pen(5)]-Enkephalin (DPDPE) is an enzymatically stable delta-opioid receptor-selective peptide, which was modified by the trimethylation of the Phe(4) residue to give beta-methyl-2', 6'-dimethylphenylalanine (TMP), resulting in four conformations : (2R,3S)-beta-Phe-DPDPE, (2R,3R)-beta-Phe-DPDPE, (2R, 3S)-beta-Phe-DPDPE, and (2S,3R)-beta-Phe-DPDPE. Synthesis was by solid-phase techniques using enantiomerically pure amino acids to give the four optically pure diastereoisomer peptides. The potency and selectivity (delta- versus mu-opioid receptor) were evaluated by radioreceptor binding in rat brain, with a mu/delta ratio decrease for all TMP conformations, compared with the parent compound (DPDPE).

The efficacy of delta-opioid receptor-selective drugs.

Delta-opioid receptor-selective drugs may provide an alternative to mu-opioid-selective drugs currently used for the relief of pain. To develop improved delta-opioid receptor-selective drugs, better measures of drug activity are necessary. In this review we suggest that efficacy calculations provide a superior measure of drug activity as compared to dissociation constants and drug potencies in functional assays.