No abstract

A mixed-metal supramolecular complex [{(bpy)2Ru(dpp)}2RhCl2]5+ has been studied and shown to undergo photoinitiated electron collection at the metal center. Reported herein is an analysis of the photochemical properties of this complex, illustrating the ability of this complex to photoreduce by two electrons by converting Rh(III) to Rh(I) and with the trimetallic assembly remaining intact. Emission-quenching experiments demonstrate efficient quenching of the Ru --> dpp charge-transfer state by the Rh center and the electron-donor dimethylaniline.

Previous studies report that microsized monosodium titanates (MSTs) deliver metal ions and species to mammalian cells and bacteria with cell-specific and metal-specific effects. In this study, we explored the use of MST and a new synthesized nanosized monosodium titanate (nMST) to deliver gold(III), cisplatin, or platinum(IV) to two human cell lines with different population doubling times, in vitro. The effect was measured using a fluorescent mitochondrial activity assay (CellTiter-Blue(®) Assay). This fluorescence assay was implemented to mitigate optical density measurement errors owing to particulate titanate interference and allowed for the studies to be extended to higher titanate concentrations than previously possible. Overall, native MST significantly (p < 0.05) decreased mitochondrial activity of both cell types by 50% at concentrations of >50 mg/L. Native nMST significantly suppressed the rapidly dividing cell line (by 50%) over untreated cultures, but had no effect on the more slowly dividing cells. For both cell types, increased titanate concentrations resulted in increased effects from delivered metals. However, there was no difference in the effect of metal delivered from micro- versus nano-sized MST.

Metal-based drugs are largely undeveloped in pharmacology. One limiting factor is the systemic toxicity of metal-based compounds. A solid-phase, sequestratable delivery agent for local delivery of metals could reduce systemic toxicity, facilitating new drug development in this nascent area. Amorphous peroxotitanates (APT) are ion-exchange materials with high affinity for several heavy metal ions and have been proposed to deliver or sequester metal ions in biological contexts. In the current study, we tested a hypothesis that APTs are able to deliver metals or metal compounds to cells. We exposed fibroblasts (L929) or monocytes (THP1) to metal-APT materials for 72 h in vitro and then measured cellular mitochondrial activity (SDH-MTT method) to assess the biological impact of the metal-APT materials versus metals or APT alone. APT alone did not significantly affect cellular mitochondrial activity, but all metal-APT materials suppressed the mitochondrial activity of fibroblasts (by 30-65% of controls). The concentration of metal-APT materials required to suppress cellular mitochondrial activity was below that required for metals alone, suggesting that simple extracellular release of the metals from the metal-APT materials was not the primary mechanism of mitochondrial suppression. In contrast to fibroblasts, no metal-APT material had a measurable effect on THP1 monocyte mitochondrial activity, despite potent suppression by metals alone. This latter result suggested that "biodelivery" by metal-APT materials may be cell type-specific. Therefore, it appears that APTs are plausible solid-phase delivery agents of metals or metal compounds to some types of cells for potential therapeutic effect.

Sodium titanates are ion-exchange materials that effectively bind a variety of metal ions over a wide pH range. Sodium titanates alone have no known adverse biological effects but metal-exchanged titanates (or metal titanates) can deliver metal ions to mammalian cells to alter cell processes in vitro. In this work, we test a hypothesis that metal-titanate compounds inhibit bacterial growth; demonstration of this principle is one prerequisite to developing metal-based, titanate-delivered antibacterial agents. Focusing initially on oral diseases, we exposed five species of oral bacteria to titanates for 24 h, with or without loading of Au(III), Pd(II), Pt(II), and Pt(IV), and measuring bacterial growth in planktonic assays through increases in optical density. In each experiment, bacterial growth was compared with control cultures of titanates or bacteria alone. We observed no suppression of bacterial growth by the sodium titanates alone, but significant (p < 0.05, two-sided t-tests) suppression was observed with metal-titanate compounds, particularly Au(III)-titanates, but with other metal titanates as well. Growth inhibition ranged from 15 to 100% depending on the metal ion and bacterial species involved. Furthermore, in specific cases, the titanates inhibited bacterial growth 5- to 375-fold versus metal ions alone, suggesting that titanates enhanced metal-bacteria interactions. This work supports further development of metal titanates as a novel class of antibacterials.

Amorphous peroxotitantes (APT) are insoluble titanium-based particles that bind a variety of metal compounds with high affinity; these particles could be sequestered locally in a solid phase to deliver metal-based drugs. Previous studies have confirmed the 'biodelivery' of metals from metal-APT complexes to fibroblasts, but not monocytes. Our goal in the current study was to use monocytic cytokine secretion to assess delivery of gold or platinum-based compounds from APT to human THP1 monocytes. Cytokine secretion was not triggered by APT alone or metal-APT complexes. In monocytes activated by lipopolysaccharide (LPS), APT alone enhanced or suppressed IL1beta or IL6 secretion, yet TNFalpha secretion was unaffected. Complexes of APT and Au(III) or cis-platin altered LPS-activated IL6 or IL1beta secretion most, TNFalpha least. Our results suggest that the APT deliver metals to monocytes.

The chemical stability, sulfur dioxide transport, ionic conductivity, and electrolyzer performance have been measured for several commercially available and experimental proton exchange membranes (PEMs) for use in a sulfur dioxide depolarized electrolyzer (SDE). The SDE's function is to produce hydrogen by using the Hybrid Sulfur (HyS) Process, a sulfur based electrochemical/thermochemical hybrid cycle. Membrane stability was evaluated using a screening process where each candidate PEM was heated at 80 °C in 60 wt. % H 2 SO 4 for 24 hours. Following acid exposure, chemical stability for each membrane was evaluated by FTIR using the ATR sampling technique. Membrane SO 2 transport was evaluated using a two-chamber permeation cell. SO 2 was introduced into one chamber whereupon SO 2 transported across the membrane into the other chamber and oxidized to H 2 SO 4 at an anode positioned immediately adjacent to the membrane. The resulting current was used to determine the SO 2 flux and SO 2 transport.Additionally, membrane electrode assemblies (MEAs) were prepared from candidate membranes to evaluate ionic conductivity and selectivity (ionic conductivity vs. SO 2 transport) which can serve as a tool for selecting membranes. MEAs were also performance tested in a HyS electrolyzer measuring current density versus a constant cell voltage (1V, 80 °C in SO 2 saturated 30 wt% H 2 SO 4 ). Finally, candidate membranes were evaluated considering all measured parameters including SO 2 flux, SO 2 transport, ionic conductivity, HyS electrolyzer performance, and membrane stability. Candidate membranes included both PFSA and non-PFSA polymers and polymer blends of which the non-PFSA polymers, BPVE-6F and PBI, showed the best selectivity.

No abstract