Investigation of the electronic, photosubstitution, redox, and surface properties of new ruthenium(II)-containing amphiphiles.

A series of pyridine- and phenol-based ruthenium(II)-containing amphiphiles with bidentate ligands of the following types are reported: [(L(PyI))Ru(II)(bpy)(2)](PF(6))(2) (1), [(L(PyA))Ru(II)(bpy)(2)](PF(6))(2) (2), [(L(PhBuI))Ru(II)(bpy)(2)](PF(6)) (3), and [(L(PhClI))Ru(II)(bpy)(2)](PF(6)) (4). Species 1 and 2 are obtained by treatment of [Ru(bpy)(2)Cl(2)] with the ligands L(PyI) (N-(pyridine-2-ylmethylene)octadecan-1-amine) and L(PyA) (N-(pyridine-2-ylmethyl)octadecan-1-amine). The imine species 3 and 4 are synthesized by reaction of [Ru(bpy)(2)(CF(3)SO(3))(2)] with the amine ligands HL(PhBuA) (2,4-di-tert-butyl-6-((octadecylamino)methyl)phenol), and HL(PhClA) (2,4-dichloro-6-((octadecylamino)methyl)phenol).

Oxidation of glutathione by [Fe(IV)(O)(N4Py)](2+): characterization of an [Fe(III)(SG)(N4Py)](2+) intermediate.

The mechanism of glutathione (GSH) oxidation by a nonheme ferryl species has been investigated. The reaction of [Fe(IV)(O)(N4Py)](2+) (1) with GSH in an aqueous solution leads to the rapid formation of a green intermediate, characterized as the low-spin ferric complex [Fe(III)(SG)(N4Py)](2+) (2) by UV-vis and electron paramagnetic resonance spectroscopies and by high-resolution time-of-flight mass spectrometry. Intermediate 2 decays to form the final products [Fe(II)(OH(2))(N4Py)](2+) and the disulfide GSSG over time.

Stability of a ferryl-peptide conjugate is controlled by a remote substituent.

The formation of a synthetic ferryl-peptide conjugate and mechanistic studies that elucidate its mode of decomposition are presented. A ferryl species is generated from a ligand-dipeptide conjugate 4. The ferryl species [Fe(IV)(4)(O)](2+), noted as compound 5, was characterized by UV-vis spectroscopy and by high-resolution electrospray mass spectrometry.

Metals in anticancer therapy: copper(II) complexes as inhibitors of the 20S proteasome.

Selective 20S proteasomal inhibition and apoptosis induction were observed when several lines of cancer cells were treated with a series of copper complexes described as [Cu(L(I))Cl] (1), [Cu(L(I))OAc] (2), and [Cu(HL(I))(L(I))]OAc (3), where HL(I) is the ligand 2,4-diiodo-6-((pyridine-2-ylmethylamino)methyl)phenol. These complexes were synthesized, characterized by means of ESI spectrometry, infrared, UV-visible and EPR spectroscopies, and X-ray diffraction when possible. After full characterization species 1-3 were evaluated for their ability to function as proteasome inhibitors and apoptosis inducers in C4-2B and PC-3 human prostate cancer cells and MCF-10A normal cells.

Structural and electronic behavior of unprecedented five-coordinate iron(III) and gallium(III) complexes with a new phenol-rich electroactive ligand.

A new asymmetric pentadentate ligand was designed to impose low symmetry to trivalent ions. Five-coordinate Fe3+ and Ga3+ complexes were investigated by crystallographic, electrochemical, and electron paramagnetic resonance methods showing enhanced redox reversibility. Calculations were performed to account for the observed trends.

Influence of ligand rigidity and ring substitution on the structural and electronic behavior of trivalent iron and gallium complexes with asymmetric tridentate ligands.

Species 1-6 are [M(III)(L)2]ClO4 complexes formed with the PhO--CH=N-CH2-Py imines, (L(I))- and (L(tBuI))-, and PhO--CH2-NH-CH2-Py amines, (L(A))- and (L(tBuA))-, in which PhO- is a phenolate ring and Py is a pyridine ring and the prefix tBu indicates the presence of tertiary butyl groups occupying the positions 4 and 6 of the phenol ring. Monometallic species with d5 high-spin iron (1, 2, 3, 4) and d10 gallium (5, 6) were synthesized and characterized to assess the influence of the ligand rigidity and the presence of tertiary butyl-substituted phenol rings on their steric, electronic, and redox behavior. Characterization by elemental analysis, mass spectrometry, IR, UV-visible, and EPR spectroscopies, and electrochemistry has been performed, and complexes [FeIII(L(tBuI))2]ClO4 (2), [FeIII(L(tBuA))2]ClO4 (4), and [Ga(III)(L(tBuI))2]ClO4 (5) have been characterized by X-ray crystallography.

Identification of colchicine in placental blood from patients using herbal medicines.

While characterizing natural antiinflammatory substances in human placental blood, we discovered a factor that affected human neutrophils and their adherence. Rigorous chemical and stereochemical analyses revealed this factor to be the well-known alkaloid, colchicine. When samples from individual patients were analyzed, significant levels (49-763 microg/L) of colchicine could be found in placental blood of patients using nonprescription herbal dietary supplements during pregnancy.

Electron/atom transfer in halo-bridged homobimetallic complexes. structure and donor-acceptor properties of face-to-face dicopper complexes with teraazamacrocyclic ligands.

The syntheses and donor-acceptor properties of some novel, halo-bridged dicopper(II) complexes of alpha,alpha'-bis(5,7-dimethyl-1,4,8,11-tetraazacyclotetradecane-6-yl)-o-xylene are reported. These complexes were characterized by their magnetic and electrochemical behavior, X-ray structure analysis, FAB mass spectroscopy, and electronic spectra. The bromo-bridged complex crystallized in the tetragonal system, space group P4(3)2(1)2, with a = 12.

A new metabolic pathway for N,N-dimethyltryptamine.

N,N-Dimethyltryptamine (DMT) undergoes a major structural alteration when added to whole human blood or its red blood cells in vitro. A new high-pressure liquid chromatography (HPLC) peak is present in extracts of these treated tissues. The compound responsible for this peak has been identified by ultraviolet spectrophotometry and by mass spectrometry as dimethylkynuramine (DMK).

Differential effect of carbidopa on the concentration of rat pineal and hypothalamic indoleamines.

Carbidopa, an aromatic acid decarboxylase inhibitor, has been shown to significantly decrease the pineal concentration of melatonin, N-acetyl serotonin (NAS), serotonin (5-HT), and 5-hydroxyindoleacetic acid (5-HIAA) but not the hypothalamic concentrations of these indoles. Increased levels of 5-hydroxytryptophan (5-HTP) indicate that carbidopa directly inhibits 5-HTP decarboxylation, thus limiting 5-HT production. Possible practical implications of selective inhibition of pineal indoleamines by carbidopa are discussed.

Objective personality assessment of children: an exploratory study of the Personality Inventory for Children (PIC) in a child psychiatric setting.

Some initial data are presented on the clinical utility of a new multidimensional objective personality inventory, the Personality Inventory for Children (PIC), Tabulation of symptoms and family characteristics independently derived from the chart data generated by 79 preadolescent outpatient evaluations resulted in an average of 12 correlates for each of the 16 profile scales. These correlates provided substantial support for the basic interpretive intent of at least 14 of these scales, as well as additional serendipitous construct validity in the form of PIC scale-parent descriptor relationships. The presentation of case findings of two adolescents with dissimilar PIC profiles demonstrated the potential value of this diagnostic instrument.