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Characterizing the geometric and electronic structures of individual photoexcited dye molecules in solution is an important step towards understanding the interfacial properties of photo-active electrodes. The broad family of "red sensitizers" based on osmium(II) polypyridyl compounds often undergoes small photo-induced structural changes which are challenging to characterize. In this work, X-ray transient absorption spectroscopy with picosecond temporal resolution is employed to determine the geometric and electronic structures of the photoexcited triplet state of [Os(terpy)₂](2+) (terpy: 2,2':6',2″-terpyridine) solvated in methanol. From the EXAFS analysis, the structural changes can be characterized by a slight overall expansion of the first coordination shell [OsN₆]. DFT calculations supports the XTA results. They also provide additional information about the nature of the molecular orbitals that contribute to the optical spectrum (with TD-DFT) and the near-edge region of the X-ray spectra.

The organometallic "half-sandwich" compound [Os(η(6)-p-cymene)(4-(2-pyridylazo)-N,N-dimethylaniline)I]PF6 is 49× more potent than the clinical drug cisplatin in the 809 cancer cell lines that we screened and is a candidate drug for cancer therapy. We investigate the mechanism of action of compound 1 in A2780 epithelial ovarian cancer cells. Whole-transcriptome sequencing identified three missense mutations in the mitochondrial genome of this cell line, coding for ND5, a subunit of complex I (NADH dehydrogenase) in the electron transport chain. ND5 is a proton pump, helping to maintain the coupling gradient in mitochondria. The identified mutations correspond to known protein variants (p.I257V, p.N447S, and p.L517P), not reported previously in epithelial ovarian cancer. Time-series RNA sequencing suggested that osmium-exposed A2780 cells undergo a metabolic shunt from glycolysis to oxidative phosphorylation, where defective machinery, associated with mutations in complex I, could enhance activity. Downstream events, measured by time-series reverse-phase protein microarrays, high-content imaging, and flow cytometry, showed a dramatic increase in mitochondrially produced reactive oxygen species (ROS) and subsequent DNA damage with up-regulation of ATM, p53, and p21 proteins. In contrast to platinum drugs, exposure to this organo-osmium compound does not cause significant apoptosis within a 72-h period, highlighting a different mechanism of action. Superoxide production in ovarian, lung, colon, breast, and prostate cancer cells exposed to three other structurally related organo-Os(II) compounds correlated with their antiproliferative activity. DNA damage caused indirectly, through selective ROS generation, may provide a more targeted approach to cancer therapy and a concept for next-generation metal-based anticancer drugs that combat platinum resistance.

Xenon and Iridiumhexafluoride react at temperatures above room temperature forming XeF+IrF6-. In presence of SbF5 FXe+IrSbF11- is formed. Xenon and Osmiumhexafluoride form in solution a blue charge transfer complex that cannot be isolated as a solid.

The design of polymers carrying suitable ligands for coordinating Os complexes in ligand exchange reactions against labile chloro ligands is a strategy for the synthesis of redox polymers with bound Os centers which exhibit a wide variation in their redox potential. This strategy is applied to polymers with an additional variation of the properties of the polymer backbone with respect to pH-dependent solubility, monomer composition, hydrophilicity etc. A library of Os-complex-modified electrodeposition polymers was synthesized and initially tested with respect to their electron-transfer ability in combination with enzymes such as glucose oxidase, cellobiose dehydrogenase, and PQQ-dependent glucose dehydrogenase entrapped during the pH-induced deposition process. The different polymer-bound Os complexes in a library containing 50 different redox polymers allowed the statistical evaluation of the impact of an individual ligand to the overall redox potential of an Os complex. Using a simple linear regression algorithm prediction of the redox potential of Os complexes becomes feasible. Thus, a redox polymer can now be designed to optimally interact in electron-transfer reactions with a selected enzyme.

A series of Ru(II) and Os(II) tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L1 = 4-p-methoxyphenyl-6-bromo-2-(2'- pyridyl)quinoline (mphbr-pq) and L2 = 4-p-hydroxyphenyl-6-bromo-2-(2'-pyridyl)-quinoline (hphbr-pq). The complexes studied are: [Ru(bpy)2L1](PF6)2 (C1), [Ru(bpy)2L2](PF6)2 (C2), [Os(bpy)2L1](PF6)2 (C3), [Os(bpy)2L2](PF6)2 (C4) (bpy = 2,2'-bipyridine), [Ru(dmbpy)2L1](PF6)2 (C5), [Ru(dmbpy)2L2](PF6)2 (C6), [Os(dmbpy)2L1](PF6)2 (C7), and [Os(dmbpy)2L2](PF6)2 (C8) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine). Moreover, new functionalized complexes C9-C12 were obtained by the base-catalyzed direct alkylation of C2, C4, C6, and C8 with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L1 and L2), and their Ru(II) or Os(II) complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The JH,H values have been determined for the majority of the resonances.

Here, we present two bifunctional protein building blocks that coassemble to form a bioelectrocatalytic hydrogel that catalyzes the reduction of dioxygen to water. One building block, a metallopolypeptide based on a previously designed triblock polypeptide, is electron-conducting. A second building block is a chimera of artificial alpha-helical leucine zipper and random coil domains fused to a polyphenol oxidase, small laccase (SLAC). The metallopolypeptide has a helix-random-helix secondary structure and forms a hydrogel via tetrameric coiled coils. The helical and random domains are identical to those fused to the polyphenol oxidase. Electron-conducting functionality is derived from the divalent attachment of an osmium bis-bipyrdine complex to histidine residues within the peptide. Attachment of the osmium moiety is demonstrated by mass spectroscopy (MS-MALDI-TOF) and cyclic voltammetry. The structure and function of the alpha-helical domains are confirmed by circular dichroism spectroscopy and by rheological measurements. The metallopolypeptide shows the ability to make electrical contact to a solid-state electrode and to the redox centers of modified SLAC. Neat samples of the modified SLAC form hydrogels, indicating that the fused alpha-helical domain functions as a physical cross-linker. The fusion does not disrupt dimer formation, a necessity for catalytic activity. Mixtures of the two building blocks coassemble to form a continuous supramolecular hydrogel that, when polarized, generates a catalytic current in the presence of oxygen. The specific application of the system is a biofuel cell cathode, but this protein-engineering approach to advanced functional hydrogel design is general and broadly applicable to biocatalytic, biosensing, and tissue-engineering applications.

The synthesis, spectroscopic characterization and X-ray crystal structure of a new chiral triosmium alkylidyne carbonyl cluster, (R,S)-[Os3(mu-H)2(CO)9{mu3-CPPh2(eta(5)-C5H4)Fe(eta(5)-C5H3(PPh2)CH(Me)NM(2)}] (1) are described. Compound 1 crystallizes in the non-centrosymmetric space group P2(1) and its absolute configuration has been established.The structure consists of an Os3C metal core with one of the PPh2 moieties of the chiral ferrocenylphosphine bonded to the apical alkylidyne carbon atom to give a zwitterionic cluster complex, reminiscent of the phosphorus ylide.

The circular dichroism spectra of the tris-bidentate metal complexes Lambda-[M(phen)3]2+, with M = Fe, Ru, Os and phen = 1,10-tris-phenanthroline, are investigated computationally, employing time-dependent density functional theory. Good agreement with experimental spectra is obtained for Ru and Os. The Lambda-[Os(phen)3]2+ spectrum is analyzed in detail. It is shown how relativistic effects red shift CD bands where the Os 5d-orbital participates to a large extent in the excitations. Further, the participation of the metal in the ligand pi --> pi exciton CD is determined to be of the order of 10%. Though solvent effects can have a noticeable effect on individual transitions and rotatory strengths, they are demonstrated to have only a very small overall effect on the resulting simulated CD spectra. For Lambda-[Fe(phen)3]2+, the results are shown to be rather sensitive to the choice of the applied hybrid and nonhybrid density functionals, and the optimized geometries based thereupon. In particular, the sign pattern of the lower-energy part (up to 33 x 10(3) cm(-1)) of the Lambda-[Fe(phen)3]2+ CD spectrum is difficult to reproduce. Some combinations of functionals and geometries yield good agreement with experiment, but no "best" approach can be devised based on the available results. Possible sources of errors in the spectrum of Lambda-[Fe(phen)3]2+ due to deficiencies in the functionals and the exchange-correlation kernels are investigated.

Results of some studies on the interaction of noble metals with quercetin (Q) and quercetin-5'-sulfonic acid (QSA), the compounds of flavonoid group, are presented. The reactions of chloride complexes of the metals: RuOHCl5(2-), PdCl4(2-), OsCl6(2-), PtCl6(2-) and AuCl4- with both reagents were examined. The redox reactions of ruthenium and gold with Q and QSA have been identified. The reaction of the metals with both reagents results in the formation of the oxidized form of Q that exhibits maximum absorbance at 291 nm. Ruthenium and gold react with the examined reagents under similar conditions: 0.04 M HCl and 1 x 10(-4) M Q (or QSA). The CH3OH + H2O (1:1) (Q) and pure aqueous (QSA) media can be used. The reaction of gold with Q is slow at room temperature. It can be accelerated by heating the solution being examined. The reaction proceeds significantly faster when the water-soluble sulfonic derivative of quercetin, quercetin-5'-sulfonic acid, is used as a reagent. The new species formed can make the basis of spectrophotometric methods for the determination of ruthenium and gold. The molar absorptivities at 291 nm are equal to 5.0 x 10(3) and 2.2 x 10(4) L mol(-1) cm(-1) for Ru and Au, respectively, independently of the reagent used. Some methods for the determination of the content of gold (0.04%) in a cosmetic cream were developed.

In order to lower the redox potentials of Os(III/II) complexes, the mixed ligand complexes of Os(II) were synthesized. The redox potentials of Os(III/II) complexes could be lowered by the use of 4,4'-dimethyl-2,2'-bipyridine (dmbpy), imidazole (Him) or its derivatives, and chloride ion as ligands, e.g., values of the redox (formal) potentials of 628 mV vs. Ag/AgCl for [Os(bpy)3]3+/2+ (bpy: 2,2'-bipyridine) and -6 mV for [OsCl(Him)(dmbpy)2]2+/+ were given in deaerated 0.1 mol dm-3 phosphate buffer (pH 7.0). The evaluation of Os(II) complexes as electron transfer mediators accessible for amperometric glucose sensors was examined according to the determination of the redox potentials of Os(III/II) complexes and the second-order rate constants for electron transfer between glucose oxidase (GOx) in reduced form and the Os(III) complex. Although the Os(II) complexes with lower redox potentials tended to decrease the second-order rate constants ks, the ks values for the majority of Os(II) complexes synthesized in this study were greater than that for ferrocenecarboxylic acid. Acceleration of the electron-transfer reaction is attributable to the hydrogen bonding and/or the electrostatic interaction between the Os(II) complexes and GOx. It may be consequently concluded that the mixed ligand complexes of Os(II) with bpy (dmbpy), Him (its derivatives), and Cl- can act as more efficient electron transfer mediators for the fabrication of amperometric glucose sensors.