Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover-the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN-;) ligands and one 2,2′-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN)4(bpy)]2-. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. We conclude that the MLCT excited state of [Fe(CN)4(bpy)]2- decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2′-bipyridine)3]2+ by more than two orders of magnitude

Ligand manipulation of charge transfer excited state relaxation and spin crossover in [Fe(2,2'-bipyridine)_2(CN)_2]

We have used femtosecond resolution UV-visible and Kβ x-ray emission spectroscopy to characterize the electronic excited state dynamics of [Fe(bpy)_2(CN)_2], where bpy=2,2'-bipyridine, initiated by metal-to-ligand charge transfer (MLCT) excitation. The excited-state absorption in the transient UV-visible spectra, associated with the 2,2'-bipyridine radical anion, provides a robust marker for the MLCT excited state, while the transient Kβ x-ray emission spectra provide a clear measure of intermediate and high spin metal-centered excited states. From these measurements, we conclude that the MLCT state of [Fe(bpy)_2(CN)_2] undergoes ultrafast spin crossover to a metal-centered quintet excited state through a short lived metal-centered triplet transient species. These measurements of [Fe(bpy)_2(CN)_2] complement prior measurement performed on [Fe(bpy)_3]^(2+) and [Fe(bpy)_4(CN)]^(2-) in dimethylsulfoxide solution and help complete the chemical series [Fe(bpy)_N(CN)_(6-2N)]^(2N-4), where N = 1-3. The measurements confirm that simple ligand modifications can significantly change the relaxation pathways and excited state lifetimes and support the further investigation of light harvesting and photocatalytic applications of 3 transition metal complexes

Mitochondrial physiology

As the knowledge base and importance of mitochondrial physiology to evolution, health and disease expands, the necessity for harmonizing the terminology concerning mitochondrial respiratory states and rates has become increasingly apparent. The chemiosmotic theory establishes the mechanism of energy transformation and coupling in oxidative phosphorylation. The unifying concept of the protonmotive force provides the framework for developing a consistent theoretical foundation of mitochondrial physiology and bioenergetics. We follow the latest SI guidelines and those of the International Union of Pure and Applied Chemistry (IUPAC) on terminology in physical chemistry, extended by considerations of open systems and thermodynamics of irreversible processes. The concept-driven constructive terminology incorporates the meaning of each quantity and aligns concepts and symbols with the nomenclature of classical bioenergetics. We endeavour to provide a balanced view of mitochondrial respiratory control and a critical discussion on reporting data of mitochondrial respiration in terms of metabolic flows and fluxes. Uniform standards for evaluation of respiratory states and rates will ultimately contribute to reproducibility between laboratories and thus support the development of data repositories of mitochondrial respiratory function in species, tissues, and cells. Clarity of concept and consistency of nomenclature facilitate effective transdisciplinary communication, education, and ultimately further discovery

Dances with Social Robots: A Pilot Study at Long-Term Care

Dance therapy can have significant physical, emotional and cognitive benefits for older adults. In particular, social robots can be developed to autonomously facilitate dance sessions to engage these individuals with the aim of improving quality of life. To successfully integrate and promote long-term use of social robots into long-term care homes for such recreational activities, it is important to explore both residents’ and staff’s perceptions of such robots. In this paper, we present the first pilot human–robot interaction study that investigates the overall experiences and attitudes of both residents and staff in a long-term care home for robot-facilitated dance sessions. In general, the questionnaire results from our study showed that both staff and residents had positive attitudes towards the robot-facilitated dance activity. Encouraging trends showed residents had higher ratings for statements on perceived ease of use, safety, and enjoyment than the staff. However, the staff had a statistically significantly higher rating for willingness to use the robots for dance facilitation. Some key statistical differences were also determined with respect to: (1) gender within the resident group (men had higher ratings for the robots being useful in helping facilitate recreational activities), as well as between staff and residents (resident men had higher perceived safety), and (2) prior robot experience (residents with limited prior experience had higher ratings on perceived ease of use and perceived enjoyment than staff with the same level of experience). The robot-facilitated dance activity was positively received by both older adults and staff as an activity of daily living that can enhance wellbeing while also being safe, easy to use and enjoyable

The structural, optical and thermoelectric properties of single target sputtered Cu2ZnSn(S,Se)(4) thin film

International audienceCu2ZnSn(S,Se)(4) (CZTSSe) thin film was fabricated by radio frequency magnetron sputtering single CZTSSe target without post-selenization or sulfuration. The formation of kesterite-type CZTSSe films with a nearly stoichiometric composition after in-situ annealing at 673 K can be achieved. The valence of the elements in CZTSSe films are Cu(I), Zn(II), Sn(IV), S(-II) and Se(-II). Optical transmission and absorption spectroscopy measurement reveal high absorption and the energy band gap is about 1.44 eV. The CZTSSe thin film is of p-type conductivity and high Seebeck coefficient value is of 450 mu V/K

Small mammals as a bioindicator of mercury in a biodiversity hotspot – The Hengduan Mountains, China

Due to toxicities, capacities for long-range transportation, bioaccumulation, and biomagnification, mercury (Hg) presents a unique concern to wildlife in remote ecosystems, including “the roof of the world”. Large carnivorous predators are thought to be exposed to elevated Hg due to their high trophic positions, but the direct assessment for Hg contamination is a challenge. Given the poorly understood Hg exposure in these carnivores, establishing a reliable and straightforward assessment would be essential to identify targeted species at Hg exposure risk for effective conservation, particularly in fragile biodiversity hotspots. Small mammals are abundant and serve as prey for large top predators. Combined with local observations, we provided an assessment to estimate the daily Hg exposure via consumption of small mammals for large carnivorous mammals recorded in the Hengduan Mountains, a world biodiversity hotspot, China. Within an altitude span from 2043 to 4251 m a.s.l., the average topsoil total mercury concentration (hereafter [THg]) was 44.65 ± 25.80 μg/kg (mean ± sd; 10.54 – 135.15 μg/kg, n = 41), while the hair [THg] in small mammals was 104.66 ± 91.96 μg/kg (mean ± sd; 7.73 to 385.70 μg/kg, n = 13). Furthermore, the daily intake of Hg was calculated among the 22 investigated/historical-recorded carnivore mammals belonging to 5 families. We found a large variance in daily intake of Hg via small mammals: Felidae (median: 205.93 μg/day) > Ursidae (135.02 μg/day) > Canidae (92.92 μg/day) > Viverridae (19.88 μg/day) > Mustelidae (7.18 μg/day). Specifically, Tiger Panthera tigris was found with the highest Hg daily intake (1701.39 μg/day) via consuming small mammals, while species belonging to Mustelidae generally have low Hg daily intake (<3 μg/day). This study provides a feasible approach to identifying species at environmental Hg risk in this fragile remote high-elevation region. The limitations and future improvements were discussed

Extrahepatic Angiogenesis: A Potential Common Pathophysiological Basis of Multiple Organ Dysfunction in Rats with Cholestasis Cirrhosis

Background: In addition to intrahepatic angiogenesis, patients with cholestasis cirrhosis develop extrahepatic vasculature disorders and functional disturbances of multiple organ systems. Without effective intervention, these vascular disorders will eventually turn into multiple organs vascular syndromes, including the brain, lung and other organ systems. However, studies on the pathogenesis of vascular alterations among extrahepatic organ disturbances are still carried out separately, which hampered the successful translation of preclinical studies to the human setting and required further mechanistic insight into these complications. This study aims to investigate the relationship between extrahepatic angiogenesis and multiple organ impairment, and whether the vascular endothelial growth factor (VEGF) family members and their receptors are involved in this process. Methods: Pathological changes of the multiple organs were determined by histopathological and immunohistochemical staining in the established common bile duct ligation (CBDL) rats, and angiogenesis was estimated by microvessel density (MVD). Levels of the VEGF family members and their receptors in the serum and organ tissues were also measured by using enzyme-linked immunosorbent assays. Results: The MVD and VEGF family members and their receptors were significantly increased in CBDL rats with multiple organ injury, especially in the liver, lung and cerebral cortex. Meanwhile, we noticed moderate elevation of soluble receptor of the vascular endothelial growth factor-1 (sFlt-1) in the liver, lung, and cerebral cortex, whereas the levels of placental growth factor (PLGF) increased significantly. Conclusions: Extrahepatic angiogenesis may represent a common pathophysiological basis for multiple organ dysfunction and the sFlt-1/PLGF ratio could offer an avenue for further studies to target extrahepatic angiogenesis in cholestatic cirrhosis