A general synthetic strategy for yolk-shell nanocrystal@ZIF-8 nanostructures has been developed. The possess the functions of nanoparticle cores, microporous shells, and a cavity in between, which offer great potential heterogeneous catalysis. involved first coating nanocrystal cores with layer Cu(2)O as sacrificial template then polycrystalline ZIF-8. clean surface assists formation ZIF-8 is etched off spontaneously simultaneously during this process. were characterized by transmission...

Differential electrochemical mass spectrometry (DEMS) analysis of the oxygen isotopologues produced by 18O-labeled Co-OEC in H216O reveals that water splitting catalysis proceeds a mechanism involves direct coupling between oxygens bound to dicobalt edge sites Co-OEC. The site chemistry has been probed using dinuclear cobalt complex. 17O NMR spectroscopy shows ligand exchange OH/OH2 at Co(III) is slow, which also confirmed DEMS experiments In borate (Bi) and phosphate (Pi) buffers, anions...

Abstract The effect of lattice strain on the catalytic properties Pd nanoparticles is systematically studied. Synthetic strategies for preparation a series shape‐controlled nanocrystals with generated from different sources has been developed. All these were created same capping agent under similar reaction conditions. First, was synthesized that enclosed in {111} surfaces: Single‐crystalline octahedra, single‐crystalline AuPd core–shell and twinned icosahedra. Next, various {100}‐terminated...

Developing syntheses of more sophisticated nanostructures comprising late transition metals broadens the tools to rationally design suitable heterogeneous catalysts for chemical transformations. Herein, we report a synthesis Pd-Rh nanoboxes by controlling migration in core-shell nanoparticle. The nanobox structure is grid-like arrangement two distinct metal phases, and surfaces these boxes are {100} dominant Pd Rh. catalytic behaviors particles were examined electrochemistry investigate...

The formation of high-valent states is a key factor in making highly active transition-metal-based catalysts the oxygen evolution reaction (OER). These high oxidation will be strongly influenced by local geometric and electronic structures metal ion, which are difficult to study due spectroscopically complex backgrounds, short lifetimes, limited concentrations. Here, we use wide range complementary X-ray spectroscopies coupled DFT calculations Co(III)4O4 cubanes their first oxidized...

The selective four electron, proton, electrochemical reduction of O2 to H2O in the presence a strong acid (TFA) is catalyzed at dicobalt center. faradaic efficiency oxygen reaction (ORR) furnished from systematic study by using rotating ring disk electrode (RRDE) methods over wide potential range. We derive thermodynamic cycle that gives access standard organic solvents, taking into account an exogenous proton donor. difference ORR selectivity for vs H2O2 depends on as dictated pKa model...

Significance The Co-OEC (oxygen-evolving catalyst) is an exemplary OEC that has provided a wealth of kinetics information on the proton-coupled electron transfer mechanism O–O bond formation. Whereas electrochemical studies establish high-valent Co(IV) 2 oxidation state as prerequisite for catalysis, this species cannot be spectroscopically examined in thin-film Co-OECs owing to its short lifetime and dilution against largely Co(III) background. A molecular model active provisioned form...

Metal nanocrystals (NCs) comprising rhodium are heterogeneous catalysts for CO oxidation, NO reduction, hydrogenations, electro-oxidations, and hydroformylation reactions. It has been demonstrated that control of structure at the nanoscale can enhance performance a metal catalyst, such as Rh, but molecular-level NCs this is less studied compared to gold, silver, platinum, palladium. We report an iodide-mediated epitaxial overgrowth Rh by using surfaces well-defined foreign crystals...

Bimetallic nanoparticle catalysts provide enhanced activity, as combining metals allows tuning of electronic and geometric structure, but the enhancement may vary during reaction because nanoparticles can undergo metal migration under catalytic conditions. Using cyclic voltammetry to track surface composition over time, we carried out a detailed study in well-defined model Au–Pd core–shell nanocatalyst. When subjected electrochemical conditions, Au from core shell was observed. The effect Pd...

The conductivities of thin film cobalt oxygen evolving catalysts (Co-OECs) are examined for four variants differing in phosphate and borate anion compositions pH. effects these parameters on the Co-OEC activity is explored by (a) examination intermediate range structural order within films through high energy X-ray scattering pair distribution function analysis, (b) direct measurement conductivity, which has been measured with an interdigitated array microelectrode. We find that nature a...

Abstract Aims Beyond causing physical discomfort, overactive bladder (OAB) is distressing to patients across a variety of psychosocial domains. In this qualitative component larger mixed methods study, we explore patients' lived experience with OAB understand how condition impacts individuals on personal and social level, as well their experiences interacting the health care system. Methods A total 20 12 physicians completed questionnaire semi‐structured interview. The interview guide,...

Significance Small-molecule conversions important to contemporary energy science often involve the reaction of two substrates in a multielectron redox process. The design catalysts effect such reactions requires knowledge mechanism. It was shown over 30 y ago that quantitative kinetics information may be extracted from cyclic voltammograms promote involving single electron and substrate. Attempts extend this model multielectron, multisubstrate have permitted only qualitative insights...

We investigated lattice strain on alloyed surfaces using ∼10 nm core-shell nanoparticles with controlled size, shape, and composition. developed a wet-chemistry method for synthesizing small octahedral PdPt alloy Au@PdPt Pd-Pt shells Au cores. Upon introduction of the core, size shape overall nanostructure composition were maintained, enabling use electrooxidation formic acid as probe to compare surface structures different strain. have found that structure is indeed impacted by generated...

Abstract Aims Overactive bladder management includes multiple therapeutic options with comparable efficacy but a range of administration modalities and side effects, creating an ideal setting for shared decision‐making. This study investigates patient physician health beliefs surrounding decision‐making expectations overactive the aim better understanding ultimately improving in care. Methods Patient participants completed questionnaire followed by semi‐structured interview to assess...

Fire departments play a critical role in responding to potential hazards generated by natural gas and propane leaks, yet the costs of providing these services is unknown. Here, we analyzed 15 years leak-coded incidents from National Incident Reporting System (NFIRS) estimated associated using fire department operating budgets. From 2003 2018, total 2.4 million required responses, accounting for ∼0.8% all nationwide incidents. Reported leak have steadily increased nationwide, nearly...

Blood cultures are the primary method for diagnosing bloodstream infections. However, blood culture contamination (BCC) can lead to unnecessary antibiotic treatment, additional tests, and extended patient time in hospital. The aim of this quality improvement project was evaluate healthcare workers’ knowledge collection protocols rates laboratory non-laboratory staff. We performed a retrospective review contaminated between May 2021 April 2022, anonymous surveys were distributed assess staff...

Background: Multiple skin-sparing incisions are utilized in immediate post-mastectomy breast reconstruction; however, the Wise pattern incision (WPI) may have superior cosmetic outcomes for large ptotic breasts compared to non-Wise (NWPI). We evaluated patient demographics and surgical with WPI versus NWPI. Methods: An electronic medical record search was performed patients at a single academic institution from 2019 2022 ICD-10-CM diagnosis code “Z42.1: encounter reconstruction following...

The mechanism of oxygen activation at a dicobalt bis-μ-hydroxo core is probed by the implementation synthetic methods to isolate reaction intermediates.

The development of heterogeneous catalysts to affect the activation recalcitrant biomolecules has applications for biomass processing, fuel cells, and wastewater remediation. We demonstrate that a cobalt oxygen evolution catalyst (Co-OEC) can catalyze oxidation carbon feedstocks completely CO2. A quantitative analysis product distribution from oxidative degradation C2 compound, ethylene glycol, is elaborated reaction sequence proposed. Co-OEC also found be competent oxidatively degrading C2+...

Extraskeletal myxoid chondrosarcoma (EMC) is an ultrarare soft tissue sarcoma, and a limited number of studies are published regarding its clinical course efficacy treatment. The goal this retrospective case series to explore patient characteristics, treatment approaches, oncologic outcomes help inform future EMC management.All patients with diagnosis seen at the University Michigan Sarcoma Center between 1998 2021 were identified. A chart review was performed analyze demographics, tumor...