Intersystem Crossing and Triplet Dynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer.

The electronic excited states of the iron(II) complex [FeII(tpy)(pyz-NHC)]2+ [tpy = 2,2':6',2″-terpyridine; pyz-NHC = 1,1'-bis(2,6-diisopropylphenyl)pyrazinyldiimidazolium-2,2'-diylidene] and their relaxation pathways have been theoretically investigated. To this purpose, trajectory surface-hopping simulations within a linear vibronic coupling model including a 244-dimensional potential energy surface (PES) with 20 singlet and 20 triplet coupled states have been used. The simulations show that, after excitation to the lowest-energy absorption band of predominant metal-to-ligand charge-transfer character involving the tpy ligand, almost 80% of the population undergoes intersystem crossing to the triplet manifold in about 50 fs, while the remaining 20% decays through internal conversion to the electronic ground state in about 300 fs. The population transferred to the triplet states is found to deactivate into two different regions of the PESs, one where the static dipole moment is small and shows increased metal-centered character and another with a large static dipole moment, where the electron density is transferred from the tpy to pyz-NHC ligand. Coherent oscillations of 400 fs are observed between these two sets of triplet populations, until the mixture equilibrates to a ratio of 60:40. Finally, the importance of selecting suitable normal modes is highlighted-a choice that can be far from straightforward in transition-metal complexes with hundreds of degrees of freedom.

Excited-State Kinetics of an Air-Stable Cyclometalated Iron(II) Complex.

The complex class [Fe(N^N^C)(N^N^N)]+ with an Earth-abundant metal ion has been repeatedly suggested as a chromophore and potential photosensitizer on the basis of quantum chemical calculations. Synthesis and photophysical properties of the parent complex [Fe(pbpy)(tpy)]+ (Hpbpy=6-phenyl-2,2'-bipyridine and tpy=2,2':6',2''-terpyridine) of this new chromophore class are now reported. Ground-state characterization by X-ray diffraction, electrochemistry, spectroelectrochemistry, UV/Vis, and X-ray spectroscopy in combination with DFT calculations proves the high impact of the cyclometalating ligand on the electronic structure. The photophysical properties are significantly improved compared to the prototypical [Fe(tpy)2 ]2+ complex. In particular, the metal-to-ligand absorption extends into the near-IR and the 3 MLCT lifetime increases by 5.5, whereas the metal-centered excited triplet state is very short-lived.

The Connection between NHC Ligand Count and Photophysical Properties in Fe(II) Photosensitizers: An Experimental Study.

Four homo- and heteroleptic complexes bearing both polypyridyl units and N-heterocyclic carbene (NHC) donor functions are studied as potential noble metal-free photosensitizers. The complexes [FeII(L1)(terpy)][PF6]2, [FeII(L2)2][PF6]2, [FeII(L1)(L3)][PF6]2, and [FeII(L3)2][PF6]2 (terpy = 2,2':6',2″ terpyridine, L1 = 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine, L2 = 2,6-bis[3-isopropylimidazol-2-ylidene]pyridine, L3 = 1-(2,2'-bipyridyl)-3-methylimidazol-2-ylidene) contain tridentate ligands of the C^N^C and N^N^C type, respectively, resulting in a Fe-NHC number between two and four. Thorough ground state characterization by single crystal diffraction, electrochemistry, valence-to-core X-ray emission spectroscopy (VtC-XES), and high energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) in combination with ab initio calculations show a correlation between the geometric and electronic structure of these new compounds and the number of the NHC donor functions. These results serve as a basis for the investigation of the excited states by ultrafast transient absorption spectroscopy, where the lifetime of the 3MLCT states is found to increase with the NHC donor count. The results demonstrate for the first time the close interplay between the number of NHC functionalities in Fe(II) complexes and their photochemical properties, as revealed in a comparison of the activity as photosensitizers in photocatalytic proton reduction.

Exploring the intersection of hermeneutics and implementation: a scoping review.

BACKGROUND: An enduring challenge remains about how to effectively implement programs, services, or practices. Too often, implementation does not achieve its intended effectiveness, fidelity, and sustainability, even when frameworks or theories determine implementation strategies and actions. A different approach is needed. This scoping review joined two markedly different bodies of literature: implementation and hermeneutics. Implementation is usually depicted as focused, direct, and somewhat linear, while hermeneutics attends to the messiness of everyday experience and human interaction. Both, however, are concerned with practical solutions to real-life problems. The purpose of the scoping review was to summarize existing knowledge on how a hermeneutic approach has informed the process of implementing health programs, services, or practices. METHODS: We completed a scoping review by taking a Gadamerian hermeneutic approach to the JBI scoping review method. Following a pilot search, we searched eight health-related electronic databases using broadly stated terms such as implementation and hermeneutics. A diverse research team that included a patient and healthcare leader, working in pairs, independently screened titles/abstracts and full-text articles. Through the use of inclusion criteria and full-team dialogue, we selected the final articles and identified their characteristics, hermeneutic features, and implementation components. RESULTS: Electronic searches resulted in 2871 unique studies. After full-text screening, we retained six articles that addressed both hermeneutics and implementing a program, service, or practice. The studies varied widely in location, topic, implementation strategies, and hermeneutic approach. All addressed assumptions underpinning implementation, the human dimensions of implementing, power differentials, and knowledge creation during implementation. All studies addressed issues foundational to implementing such as cross-cultural communication and surfacing and addressing tensions during processes of change. The studies showed how creating conceptual knowledge was a precursor to concrete, instrumental knowledge for action and behavioral change. Finally, each study demonstrated how the hermeneutic process of the fusion of horizons created new understandings needed for implementation. CONCLUSIONS: Hermeneutics and implementation have rarely been combined. The studies reveal important features that can contribute to implementation success. Implementers and implementation research may benefit from understanding, articulating, and communicating hermeneutic approaches that foster the relational and contextual foundations necessary for successful implementation. TRIAL REGISTRATION: The protocol was registered at the Centre for Open Science on September 10, 2019. MacLeod M, Snadden D, McCaffrey G, Zimmer L, Wilson E, Graham I, et al. A hermeneutic approach to advancing implementation science: a scoping review protocol 2019. Accessed at osf.io/eac37.

Engaging with patients in research on knowledge translation/implementation science methods: a self study.

BACKGROUND: In 2017, the British Columbia (Canada) SUPPORT (SUpport for People and Patient-Oriented Research) Unit created six methods clusters to advance methodologies in patient and public oriented research (POR). The knowledge translation (KT)/implementation science methods cluster identified that although there was guidance about how to involve patients and public members in POR research generally, little was known about how best to involve patients and public members on teams specifically exploring POR KT/implementation science methodologies. The purpose of this self-study was to explore what it means to engage patients and the public in studies of POR methods through the reflections of members of five KT/implementation science teams. METHODS: Informed by a collaborative action research approach, this quality improvement self-study focused on reflection within four KT/implementation science research teams in 2020-2021. The self-study included two rounds of individual interviews with 18 members across four teams. Qualitative data were analyzed using a thematic analysis approach followed by a structured discussion of preliminary findings with the research teams. Subsequently, through two small group discussion sessions, the patients/public members from the teams refined the findings. RESULTS: Undertaking research on POR KT/implementation science methodologies typically requires teams to work with the uncertainty of exploratory and processual research approaches, make good matches between patients/public members and the team, work intentionally yet flexibly, and be attuned to the external context and its influences on the team. POR methodological research teams need to consider that patients/public members bring their life experiences and world views to the research project. They become researchers in their own right. Individual and team reflection allows teams to become aware of team needs, acknowledge team members' vulnerabilities, gain greater sensitivity, and enhance communication. CONCLUSIONS: The iterative self-study process provided research team members with opportunities for reflection and new understanding. Working with patients/public team members as co-researchers opens up new ways of understanding important aspects of research methodologies, which may influence future KT/implementation science research approaches.

In this self-study we aimed to understand how members of research teams work together. We explored how research teams included patients and public members in studying research approaches (methods) that support the creation, sharing, and use of research results that matter to patients and the public (patient and public-oriented research). We analyzed interviews with 18 members of 4 teams and discussed the findings with each team. We then further refined the results and their interpretation with patients/public team members. We found that research teams had to deal with the uncertainty that is common for this type of research, which is often exploratory and focuses on processes. There needed to be a good match between patient/public members, the topic, and the team. Teams had to be flexible in how they worked together and they needed to address how power was shared within the team. Finally, the teams were affected by world events such as COVID and social unrest. Research team members had a chance to reflect and gain new understandings through the self-study. A key learning was that patients and public members bring their life experiences and world views to the project. They become researchers in their own right. When team members have a chance to reflect they can become more aware of their own and others' talents, needs, and vulnerabilities, that awareness can help improve communication and teamwork. Patients and public members as co-researchers can bring new ways of understanding important features of knowledge translation and implementation science research approaches.

Bupivacaine use in the Insuflow device during laparoscopic cholecystectomy: results of a prospective randomized double-blind controlled trial.

BACKGROUND: Recent evidence [Surg Endosc (2007) 21: 602-606] demonstrates that intraperitoneal bupivacaine administered as an aerosol via a special catheter is safe and significantly decreases postoperative pain in laparoscopic surgery. We currently use the Insuflow device (Lexion Medical) routinely to warm and humidify gas in laparoscopic surgery. The purpose of this study is to determine whether using bupivacaine instead of water in existing technology already in use (Insuflow) will result in decreased postoperative pain, without increasing operative time or cost. METHODS: Using a double-blind methodology, 50 patients undergoing elective outpatient laparoscopic cholecystectomy were randomized to a study drug: either 10 ml of 0.5% bupivacaine (50 mg) or 10 ml of sterile water. The study drug was injected into the Insuflow in the standard fashion and the operation commenced routinely. No perioperative nonsteroidal anti-inflammatory drugs were used. Using a standard 0-10 pain-scoring scale, patients were assessed by perioperative nurses at 1 and 2 h postoperatively. Pain was again assessed at 24 h by telephone interview, along with the number of narcotic oral analgesics used in the first 24 h. RESULTS: Fifty patients were randomized, 25 in each group; the groups were comparable. All patients completed the study and 100% follow-up was obtained. All patients were discharged the same day and there were no significant complications in either group, and specifically no complications attributed to bupivacaine or use of the Insuflow device. There were no differences in pain at 1 and 2 h. There was less pain in the bupivacaine group at 24 h, but this was not statistically significant (P = 0.055). CONCLUSIONS: Bupivacaine use in the Insuflow device is safe. No significant differences in postoperative pain were noted in this study compared to using water.

Water structure near the surface of Weyl semimetals as catalysts in photocatalytic proton reduction.

In this work, second-generation Car-Parrinello-based mixed quantum-classical mechanics molecular dynamics simulations of small nanoparticles of NbP, NbAs, TaAs, and 1T-TaS2 in water are presented. The first three materials are topological Weyl semimetals, which were recently discovered to be active catalysts in photocatalytic water splitting. The aim of this research was to correlate potential differences in the water structure in the vicinity of the nanoparticle surface with the photocatalytic activity of these materials in light induced proton reduction. The results presented herein allow explaining the catalytic activity of these Weyl semimetals: the most active material, NbP, exhibits a particularly low water coordination near the surface of the nanoparticle, whereas for 1T-TaS2, with the lowest catalytic activity, the water structure at the surface is most ordered. In addition, the photocatalytic activity of several organic and metalorganic photosensitizers in the hydrogen evolution reaction was experimentally investigated with NbP as the proton reduction catalyst. Unexpectedly, the charge of the photosensitizer plays a decisive role for the photocatalytic performance.

Outcomes after resection of cholangiocellular carcinoma.

BACKGROUND: Cholangiocellular carcinoma (CCC) is a rare primary liver malignancy that arises from intrahepatic bile duct canaliculi and presents as a liver mass. Our purpose is to report operative morbidity and mortality and to determine long-term survival after resection for CCC. METHODS: Retrospective review of 31 consecutive patients who underwent resection during a 20-year period. RESULTS: Thirty-day hospital mortality was 3%, and postoperative morbidity was 38%. Kaplan-Meier 5-year survival was 35%; mean survival was 37 months; absolute 5-year survival was 33%. Mean survival in stages I, II, IIIA, and IIIC were 57, 33, 26, and 14 months, respectively (P = 0.03 comparing I to >I). Recurrence occurred in 18 patients; 89% were in the liver. Carbohydrate antigen 19-9 >100 U/mL was found to be an indicator of poor prognosis (P = 0.009). CONCLUSIONS: Resection for CCC can be performed with acceptable morbidity and mortality rates and results in good survival and cure. Hepatic recurrence is common. Carbohydrate antigen 19-9 may be useful in determining prognosis.

Primary squamous cell carcinoma of the thyroid gland.

A case of primary squamous cell carcinoma of the thyroid is presented. Squamous epithelium is normally not present in the thyroid gland, and this tumor is exceedingly rare. Proper workup is described, including the differentiation from metastatic disease. The case reported is of a 64-year-old woman who presented with an asymptomatic nodule and underwent thyroidectomy. The final pathologic diagnosis, confirmed using immunohistochemistry for cytokeratin and transmission electron microscopy, revealed the unusual tumor. Squamous cell carcinoma of the thyroid is highly aggressive and behaves clinically like anaplastic thyroid carcinoma; the prognosis is poor. The patient described developed local recurrence and expired 7 months after resection from local invasion and airway obstruction. Unfortunately, this is the typical outcome. Chemoradiotherapy is generally not helpful, and complete resection remains the best chance for cure.