Electronic structure theory predicts that, depending on the strength of the ligand field, either the quintet ((5)T2) or triplet ((3)T1) term states can be stabilized as the lowest-energy ligand-field excited state of low-spin octahedral d(6) transition-metal complexes. The (3)T1 state is anticipated for second- and third-row metal complexes and has been established for certain first-row compounds such as [Co(CN)6](3-), but in the case of the widely studied Fe(II) ion, only the (5)T2 state has ever been documented. Herein we report that 2,6-bis(2-carboxypyridyl)pyridine (dcpp), when bound to Fe(II), presents a sufficiently strong ligand field to Fe(II) such that the (5)T2/(3)T1 crossing point of the d(6) configuration is approached if not exceeded. The electrochemical and photophysical properties of [Fe(dcpp)2](2+), in addition to being of fundamental interest, may also have important implications for solar energy conversion strategies that seek to utilize earth-abundant components.

Identification of transient species is a necessary part of delineating the kinetics and mechanisms associated with chemical dynamics; when dealing with photo-induced processes, this can be an exceptionally challenging task due to the fact that spectra associated with excited state(s) sampled over the course of a photochemical event often cannot be uniquely identified nor readily calculated. Using Group 8 complexes of the general form [M(terpy)2](2+) and [M(bpy)3](2+) as a platform (where terpy is 2,2':6',2''-terpyridine and bpy is 2,2'-bipyridine), we demonstrate how spectroelectrochemical measurements can serve as an effective tool for identifying spectroscopic signatures of charge-transfer excited states of transition metal-based chromophores. Formulating the metal-to-ligand charge-transfer (MLCT) excited state(s) as M(3+)-L(-), the extent to which a linear combination of the spectra of the oxidized and reduced forms of the parent complexes can be used to simulate the characteristic absorptions of MLCT-based transient species is examined. Quantitative agreement is determined to be essentially unachievable due to the fact that certain transitions associated with the optically prepared excited states are either overcompensated for in the spectroelectrochemical data, or simply cannot be replicated through electrochemical means. Despite this limitation, it is shown through several illustrative examples that this approach can still be extremely useful as a qualitative if not semi-quantitative guide for interpreting time-resolved electronic absorption data of charge-transfer compounds, particularly in the ultrafast time domain.

The combination of molecular dyes and catalysts with semiconductors into dye-sensitized solar fuel devices (DSSFDs) requires control of efficient interfacial and surface charge transfer between the components. The present study reports on the light-induced electron transfer processes of p-type NiO films cosensitized with coumarin C343 and a bioinspired proton reduction catalyst, [FeFe](mcbdt)(CO)6 (mcbdt = 3-carboxybenzene-1,2-dithiolate). By transient optical spectroscopy we find that ultrafast interfacial electron transfer (τ ≈ 200 fs) from NiO to the excited C343 ("hole injection") is followed by rapid (t1/2 ≈ 10 ps) and efficient surface electron transfer from C343(-) to the coadsorbed [FeFe](mcbdt)(CO)6. The reduced catalyst has a clear spectroscopic signature that persists for several tens of microseconds, before charge recombination with NiO holes occurs. The demonstration of rapid surface electron transfer from dye to catalyst on NiO, and the relatively long lifetime of the resulting charge separated state, suggests the possibility to use these systems for photocathodes on DSSFDs.

We report on the synthesis and characterization of a donor-acceptor ruthenium polypyridyl complex as a photosensitizer for p-type dye-sensitized solar cells (DSSCs). The electrochemical, photophysical, and photovoltaic performance of two ruthenium-based photosensitizers were tested in NiO-based DSSCs; bis-(2,2'-bipyridine-4,4'-dicarboxylic acid)(2)N-(1,10-phenanthroline)-4-nitronaphthalene-1,8-dicarboximide ruthenium(II), ([Ru(dcb)(2)(NMI-phen)](PF(6))(2)) and tris-(2,2'-bipyridine-4,4'-dicarboxylic acid)(3) ruthenium(ii), [(Ru(dcb)(3))Cl(2)]. The presence of an electron-accepting group, 4-nitronaphthalene-1,8-dicarboximide (NMI), attached to the phenanthroline of [Ru(dcb)(2)(NMI-phen)](2+) resulted in long-lived charge separation between reduced [Ru(dcb)(2)(NMI-phen)](2+) and NiO valence band holes; 10-50 μs. In the reduced state for [Ru(dcb)(2)(NMI-phen)](2+), the electron localized on the distal NMI group. In tests with I(3)(-)/I(-) and Co(4,4'-di-tert-butyl-bipyridine)(3)(2+/3+) electrolytes, [Ru(dcb)(2)(NMI-phen)](2+) outperformed [Ru(dcb)(3)](2+) in solar cell efficiency in devices. A record APCE (25%) was achieved for a ruthenium photosensitizer in a p-type DSSC. Insights on photosensitizer regeneration kinetics are included.

Three new cyclometalated iridium complexes were prepared and investigated on nanocrystalline NiO cathodes. Nanosecond transient absorption spectroscopy experiments show they present a surprisingly slow geminate charge recombination upon excitation on NiO, representing thus the first examples of simple sensitizers with such feature. These complexes were used in dye-sensitized solar cells using nanocrystalline NiO film as semiconductor. The long-lived charge separated state of these Ir complexes make them compatible with other redox mediators than I3(-)/I(-), such as a cobalt electrolyte and enable to reach significantly high open circuit voltage.

Objective: To describe the natural history, treatment and cost of Ross River virus‐induced epidemic polyarthritis (RRV disease). Design: Questionnaire‐based longitudinal prospective study. Participants and setting: Patients in the greater Brisbane area, Queensland, diagnosed with RRV disease by their general practitioners based on clinical symptoms and paired serological tests between November 1997 and April 1999. Main outcome measures: Scores on two validated quality‐of‐life questionnaires (Clinical Health Assessment Questionnaire and Medical Outcomes Study Short Form 36) were obtained soon after diagnosis and one, two, three, six and 12 months thereafter. Scores were compared between patients diagnosed with RRV disease alone and those with RRV disease plus other conditions. Results: 67 patients were enrolled. Most patients with RRV disease alone had severe acute symptoms, but followed a consistent path to recovery within three to six months. Other conditions, often chronic rheumatic diseases or depression, were identified in half the cohort; their quality‐of‐life scores suggested stable chronic illness between six and 12 months after diagnosis. Non‐steroidal anti‐inflammatory drugs (NSAIDs) were taken by 58% of patients (average use, 7.6 weeks; range, 2–22 weeks). Time off work averaged 1.9 days, and direct cost to the community was estimated as $A1018 per patient. Conclusions: Symptom duration and frequency of long‐term symptoms may have been overestimated by previous studies of RRV disease. Disease persisting six to 12 months after RRV diagnosis was largely attributable to other conditions, highlighting the need to seek other diagnoses in RRV patients with persistent symptoms.

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Many studies have documented the association between mechanical deviations from normal and the presence or risk of injury. Some runners attempt to change mechanics by increasing running cadence. Previous work documented that increasing running cadence reduces deviations in mechanics tied to injury. The long-term effect of a cadence retraining intervention on running mechanics and energy expenditure is unknown. This study aimed to determine if increasing running cadence by 10% decreases running efficiency and changes kinematics and kinetics to make them less similar to those associated with injury. Additionally, this study aimed to determine if, after 6 weeks of cadence retraining, there would be carryover in kinematic and kinetic changes from an increased cadence state to a runner's preferred running cadence without decreased running efficiency. We measured oxygen uptake, kinematic and kinetic data on six uninjured participants before and after a 6-week intervention. Increasing cadence did not result in decreased running efficiency but did result in decreases in stride length, hip adduction angle and hip abductor moment. Carryover was observed in runners' post-intervention preferred running form as decreased hip adduction angle and vertical loading rate.