Understanding electrogenerated chemiluminescence efficiency in blue-shifted iridium(III)-complexes: an experimental and theoretical study.

Compared to tris(2-phenylpyridine)iridium(III) ([Ir(ppy)3 ]), iridium(III) complexes containing difluorophenylpyridine (df-ppy) and/or an ancillary triazolylpyridine ligand [3-phenyl-1,2,4-triazol-5-ylpyridinato (ptp) or 1-benzyl-1,2,3-triazol-4-ylpyridine (ptb)] exhibit considerable hypsochromic shifts (ca. 25-60 nm), due to the significant stabilising effect of these ligands on the HOMO energy, whilst having relatively little effect on the LUMO. Despite their lower photoluminescence quantum yields compared with [Ir(ppy)3 ] and [Ir(df-ppy)3 ], the iridium(III) complexes containing triazolylpyridine ligands gave greater electrogenerated chemiluminescence (ECL) intensities (using tri-n-propylamine (TPA) as a co-reactant), which can in part be ascribed to the more energetically favourable reactions of the oxidised complex (M(+) ) with both TPA and its neutral radical oxidation product. The calculated iridium(III) complex LUMO energies were shown to be a good predictor of the corresponding M(+) LUMO energies, and both HOMO and LUMO levels are related to ECL efficiency. The theoretical and experimental data together show that the best strategy for the design of efficient new blue-shifted electrochemiluminophores is to aim to stabilise the HOMO, while only moderately stabilising the LUMO, thereby increasing the energy gap but ensuring favourable thermodynamics and kinetics for the ECL reaction. Of the iridium(III) complexes examined, [Ir(df-ppy)2 (ptb)](+) was most attractive as a blue-emitter for ECL detection, featuring a large hypsochromic shift (λmax =454 and 484 nm), superior co-reactant ECL intensity than the archetypal homoleptic green and blue emitters: [Ir(ppy)3 ] and [Ir(df-ppy)3 ] (by over 16-fold and threefold, respectively), and greater solubility in polar solvents.

Farmers' Rights and Digital Sequence Information: Crisis or Opportunity to Reclaim Stewardship Over Agrobiodiversity?

Contestations about the way in which digital sequence information is used and regulated have created stumbling blocks across multiple international policy processes. Such schisms have profound implications for the way in which we manage and conceptualize agrobiodiversity and its benefits. This paper explores the relationship between farmers' rights, as recognized in the International Treaty on Plant Genetic Resources for Food and Agriculture, and the dematerialization of genetic resources. Using concepts of "stewardship" and "ownership" we emphasize the need to move away from viewing agrobiodiversity as a commodity that can be owned, toward a strengthened, proactive and expansive stewardship approach that recognizes plant genetic resources for food and agriculture as a public good which should be governed as such. Through this lens we analyze the relationship between digital sequence information and different elements of farmers' rights to compare and contrast implications for the governance of digital sequence information. Two possible parallel pathways are presented, the first envisaging an enhanced multilateral system that includes digital sequence information and which promotes and enhances the realization of farmers' rights; and the second a more radical approach that folds together concepts of stewardship, farmers' rights, and open source science. Farmers' rights, we suggest, may well be the linchpin for finding fair and equitable solutions for digital sequence information beyond the bilateral and transactional approach that has come to characterize access and benefit sharing under the Convention on Biological Diversity. Existing policy uncertainties could be seized as an unexpected but serendipitous opportunity to chart an alternative and visionary pathway for the rights of farmers and other custodians of plant genetic resources.

Fast Science and Sluggish Policy: The Herculean Task of Regulating Biodiscovery.

New rules for access and benefit sharing (ABS) of genetic resources and associated traditional knowledge have been established by the Nagoya Protocol but have not kept up with rapid scientific and technological advances in biodiscovery. This suggests the need for innovative, transdisciplinary approaches to regulate ABS and emerging technologies.

Non-Psychrophilic Methanogens Capable of Growth Following Long-Term Extreme Temperature Changes, with Application to Mars.

Although the martian environment is currently cold and dry, geomorphological features on the surface of the planet indicate relatively recent (<4 My) freeze/thaw episodes. Additionally, the recent detections of near-subsurface ice as well as hydrated salts within recurring slope lineae suggest potentially habitable micro-environments within the martian subsurface. On Earth, microbial communities are often active at sub-freezing temperatures within permafrost, especially within the active layer, which experiences large ranges in temperature. With warming global temperatures, the effect of thawing permafrost communities on the release of greenhouse gases such as carbon dioxide and methane becomes increasingly important. Studies examining the community structure and activity of microbial permafrost communities on Earth can also be related to martian permafrost environments, should life have developed on the planet. Here, two non-psychrophilic methanogens, Methanobacterium formicicum and Methanothermobacter wolfeii, were tested for their ability to survive long-term (~4 year) exposure to freeze/thaw cycles varying in both temperature and duration, with implications both for climate change on Earth and possible life on Mars.

Facility Closure: How to Get In, Get Out, and Get What Is Important.

This article examines the current state of affairs of the health information management role in facility closure as well as the impact on revenue cycle operations. Health information management professionals are uniquely positioned to assist an organization in closure efforts because of their knowledge of revenue cycle operations, ability to work with the software products used to generate and store patient information, and solid understanding of the process of care and treatment of the patient. This information is integral to ensuring that patient information in a variety of formats and locations is properly secured and saved so that it will be available to patients and caregivers who need it after the facility closes. This article also goes into detail concerning some of the financial tasks required to be completed when a facility closes because the required data come from coded information or, in the case of the Worker Adjustment and Retraining Notification (WARN) Act, affect how employees will be compensated. This article provides a detailed look at the process to help guide other health information management professionals in a diverse set of care environments in the process of facility closure.