Resonance Raman Spectro-Electrochemistry to Illuminate Photo-Induced Molecular Reaction Pathways

Electron transfer reactions play a key role for artificial solar energy conversion, however, the underlying reaction mechanisms and the interplay with the molecular structure are still poorly understood due to the complexity of the reaction pathways and ultrafast timescales. In order to investigate such light-induced reaction pathways, a new spectroscopic tool has been applied, which combines UV-vis and resonance Raman spectroscopy at multiple excitation wavelengths with electrochemistry in a thin-layer electrochemical cell to study [RuII(tbtpy)2]2+ (tbtpy = tri-tert-butyl-2,2′:6′,2′′-terpyridine) as a model compound for the photo-activated electron donor in structurally related molecular and supramolecular assemblies. The new spectroscopic method substantiates previous suggestions regarding the reduction mechanism of this complex by localizing photo-electrons and identifying structural changes of metastable intermediates along the reaction cascade. This has been realized by monitoring selective enhancement of Raman-active vibrations associated with structural changes upon electronic absorption when tuning the excitation wavelength into new UV-vis absorption bands of intermediate structures. Additional interpretation of shifts in Raman band positions upon reduction with the help of quantum chemical calculations provides a consistent picture of the sequential reduction of the individual terpyridine ligands, i.e., the first reduction results in the monocation [(tbtpy)Ru(tbtpy•)]+, while the second reduction generates [(tbtpy•)Ru(tbtpy•)]0 of triplet multiplicity. Therefore, the combination of this versatile spectro-electrochemical tool allows us to deepen the fundamental understanding of light-induced charge transfer processes in more relevant and complex systems

Unraveling the Light-Activated Reaction Mechanism in a Catalytically Competent Key Intermediate of a Multifunctional Molecular Catalyst for Artificial Photosynthesis

Understanding photodriven multielectron reaction pathways requires the identification and spectroscopic characterization of intermediates and their excited-state dynamics, which is very challenging due to their short lifetimes. To the best of our knowledge, this manuscript reports for the first time on in situ spectroelectrochemistry as an alternative approach to study the excited-state properties of reactive intermediates of photocatalytic cycles. UV/Vis, resonance-Raman, and transient-absorption spectroscopy have been employed to characterize the catalytically competent intermediate [(tbbpy)2RuII(tpphz)RhICp*] of [(tbbpy)2Ru(tpphz)Rh(Cp*)Cl]Cl(PF6)2 (Ru(tpphz)RhCp*), a photocatalyst for the hydrogenation of nicotinamide (NAD-analogue) and proton reduction, generated by electrochemical and chemical reduction. Electronic transitions shifting electron density from the activated catalytic center to the bridging tpphz ligand significantly reduce the catalytic activity upon visible-light irradiation. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Increasing effectiveness and equity in strengthening health research capacity using data and metrics: recent advances of the ESSENCE mechanism

Background: The ESSENCE on Health Research initiative established a Working Group on Review of Investments in 2018 to improve coordination and collaboration among funders of health research capacity strengthening. The Working Group comprises more than a dozen ESSENCE members, including diverse representation by geography, country income level, the public sector, and philanthropy. Objective: The overall goal of the Working Group is increased research on national health priorities as well as improved pandemic preparedness, and, ultimately, fewer countries with very limited research capacity. Methods: We developed a basic set of metrics for national health research capacity, assessed different models of coordination and collaboration, took a deeper dive into eight countries to characterize their national research capacity, and began to identify opportunities to better coordinate our investments. In this article, we summarize the presentations, discussions, and outcomes of our second annual (virtual) meeting, which had more than 100 participants representing funders, researchers, and other stakeholders from higher- and lower-income countries worldwide. Findings and conclusions: Presentations on the first day included the keynote speaker, Dr. Soumya Swaminathan, chief scientist of the World Health Organization (WHO), and updates on data and metrics for research capacity, which are critical to establish targets, road maps, and budgets. The second day focused on improving collaboration and coordination among funders and other stakeholders, the potential return on investment for health research, ongoing work to increase coordination at the country level, and examples of research capacity strengthening efforts in diverse health research areas from around the world. We concluded that an intentional data- and metric-driven approach to health research capacity strengthening, emphasizing coordination among funders, local leadership, and equitable partnerships and allocation of resources, will enhance the health systems of resource-poor countries as well as the world's pandemic preparedness

A global matchmaking web platform facilitating equitable institutional partnerships and mentorship to strengthen health workforce training capacity

The critical human resources deficit in the healthcare sector in low-resource settings (LRS) has an overwhelming impact on health outcomes and disparities in growth and development of the global healthcare workforce. There is a lack of qualified trainers and mentors and this makes it challenging to connect existing capacity gaps with existing expertise and established programs. Through global health partnerships, training programs, and mentorship, individuals and institutions from around the globe can connect to share training resources and strengthen clinical and research capacity in LRSs. Global health partnerships focused on capacity building face many challenges including; unequal access to information about potential partners and training opportunities, a lack of transparency regarding each institutions training priorities, and inequity and absent reciprocity within global health partnerships that have disproportionate power division between high-resource and LRSs. This initiative, the Consortium of Universities for Global Health Capacity Strengthening Platform (CUGH-CPS) (CUGHCapacityBuilding.org), aims to empower institutions and individuals in LRSs to address these challenges and drive partnership engagement through avenues that are beneficial to the LRS agent needs and context by leading the prioritization of training capacity development across clinical and research domains. The CUGH-CPS helps to identify and create a platform for the dissemination of training and mentorship needs from LRS institutions and share this information with the global community. This manuscript describes this new initiative officially launched to a global audience at the April 2023 CUGH meeting

Plasma Dynamics

Contains reports on five research projects.U.S. Air Force - Office of Scientifc Research (Contract AFOSR 84-0026)National Science Foundation (Grant ECS 85-14517)Lawrence Livermore National Laboratory (Subcontract 6264005)National Science Foundation (Grant ECS 85-15032)U.S. Department of Energy (Contract DE-ACO2-78-ET-51013)U.S. Department of Energy (Contract DE-ACO2-ET-51013

Plasma Dynamics

Contains table of contents for Section 2 and reports on four research projects.Lawrence Livermore National Laboratory Subcontract 6264005National Science Foundation Grant ECS 84-13173National Science Foundation Grant ECS 85-14517U.S. Air Force - Office of Scientific Research Contract AFOSR 89-0082-AU.S. Army - Harry Diamond Laboratories Contract DAAL02-86-C-0050U.S. Navy - Office of Naval Research Contract N00014-87-K-2001Lawrence Livermore National Laboratory Subcontract B108472National Science Foundation Grant ECS 88-22475U.S. Department of Energy Contract DE-FG02-91-ER-54109National Aeronautics and Space Administration Grant NAGW-2048U.S. Department of Energy Contract DE-AC02-ET-51013U.S. Department of Energy Contract DE-AC02-78-ET-5101

Plasma Dynamics

Contains table of contents for Section 2 and reports on four research projects.Lawrence Livermore National Laboratory (Subcontract 6264005)National Science Foundation (Grant ECS 84-13173)National Science Foundation (Grant ECS 85-14517)U.S. Air Force - Office of Scientifc Research (Contract AFOSR 84-0026)U.S. Army - Harry Diamond Laboratories (Contract DAAL02-86-C-0050)U.S. Navy - Office of Naval Research (Contract N00014-87-K-2001)U.S. Department of Energy (Contract DE-AC02-78-ET-51013)National Science Foundation (Grant ECS 85-1 5032

Plasma Dynamics

Contains table of contents for Section 2 and reports on four research projects.Lawrence Livermore National Laboratory Subcontract 6264005National Science Foundation Grant ECS 84-13173National Science Foundation Grant ECS 85-14517U.S. Air Force - Office of Scientific Research Contract AFOSR 84-0026U.S. Army - Harry Diamond Laboratories Contract DAAL02-86-C-0050U.S. Navy - Office of Naval Research Contract N00014-87-K-2001National Science Foundation Grant ECS 85-15032National Science Foundation Grant ECS 88-22475U.S. Department of Energy Contract DE-AC02-ET-5101

Plasma Dynamics

Contains table of contents for Section 2 and reports on four research projects.National Science Foundation Grant ECS 89-02990U.S. Air Force - Office of Scientific Research Grant AFOSR 89-0082-BU.S. Army - Harry Diamond Laboratories Contract DAAL02-89-K-0084U.S. Department of Energy Contract DE-AC02-90ER40591U.S. Navy - Office of Naval Research Grant N00014-90-J-4130Lawrence Livermore National Laboratory Subcontract B-160456National Science Foundation Grant ECS 88-22475U.S. Department of Energy Contract DE-FG02-91-ER-54109National Aeronautics and Space Administration Grant NAGW-2048U.S.-Israel Binational Science Foundation Grant 87-0057U.S Department of Energy Contract DE-AC02-78-ET-5101