Studying manganese carbonyl photochemistry in a permanently porous metal-organic framework.

Mn(diimine)(CO)3X (X = halide) complexes are critical components of chromophores, photo- and electrocatalysts, and photoactive CO-releasing molecules (photoCORMs). While these entities have been incorporated into metal-organic frameworks (MOFs), a detailed understanding of the photochemical and chemical processes that occur in a permanently porous support is lacking. Here we site-isolate and study the photochemistry of a Mn(diimine)(CO)3Br moiety anchored within a permanently porous MOF support, allowing for not only the photo-liberation of CO from the metal but also its escape from the MOF crystals. In addition, the high crystallinity and structural flexibility of the MOF allows crystallographic snapshots of the photolysis products to be obtained. We report these photo-crystallographic studies in the presence of coordinating solvents, THF and acetonitrile, showing the changing coordination environment of the Mn species as CO loss proceeds. Using time resolved experiments, we report complementary spectroscopic studies of the photolysis chemistry and characterize the final photolysis product as a possible Mn(ii) entity. These studies inform the chemistry that occurs in MOF-based photoCORMs and where these moieties are employed as catalysts.

"Breaking" the Emergency Department: Does the Culture of Emergency Medicine Present a Barrier to Self-Care?

INTRODUCTION: Our goal was to critically examine emergency physician's (EP) beliefs about taking breaks for self-care on shift. Our operational definition of a break for self-care included time not engaging in direct patient care, eating, drinking, using the bathroom, or leaving a clinical area for a mental break. Using focus groups, the study aimed to accomplish the following: 1) identify barriers to why residents and faculty at our academic center may not take breaks in the emergency department; 2) generate hypotheses for empirical testing; and 3) generate solutions to include in a departmental breaks initiative. METHODS: We convened eight focus groups comprised separately of resident and faculty physicians. Group discussion was guided by eight questions representing a priori themes. The groups were recorded for transcription and subjected to a "cut-and-sort" process. Six themes were identified by consensus after independent review by three of the co-authors, which were confirmed by participant validation. RESULTS: We identified six themes that represented the pooled outcomes of both resident and faculty focus groups: 1) Physiological needs affect clinical performance, 2) EPs share beliefs around taking breaks that center on productivity, patient safety and the dichotomy of strength/weakness, 3) when taking breaks EPs fear worst-case scenarios, 4) breaking is a learned skill, 5) culture change is needed to allow EPs to engage in self-care; and 6) a flexible, individualized approach to breaking is necessary. Our central finding was that productivity and patient safety are of key importance to EPs when considering whether to take a break for self-care. We identified a dichotomy with the concept of strength related to productivity/patient safety, and the concept of weakness related to self-care. CONCLUSION: The current practice culture of emergency medicine and the organization of our unique work environment may present barriers to physicians attempting to engage in self-care.

Mystery of neck lump: an uncommon presentation of urachal cancer.

We present the case of a 55-year-old male patient who presented with palpable cervical lymphadenopathy. Excisional biopsy showed metastatic adenocarcinoma of unknown origin. Imaging showed a bladder mass following which he underwent transurethral resection of bladder tumour. Histopathological evaluation of mass confirmed a poorly differentiated adenocarcinoma with signet-ring cell features. Immunohistochemistry was suggestive of metastatic urachal cancer. He agreed for enrollment in a clinical trial, however soon after 1st cycle, he developed immune pneumonitis requiring high dose steroids. On follow-up, MRI brain was done for evaluation of headache which showed metastatic intracranial disease. He completed radiotherapy following which he was started on FOLFOX chemo regimen (folinic acid, 5-fluorouracil and oxaliplatin).