Porphyrin-fused graphene nanoribbons.

Graphene nanoribbons (GNRs), nanometre-wide strips of graphene, are promising materials for fabricating electronic devices. Many GNRs have been reported, yet no scalable strategies are known for synthesizing GNRs with metal atoms and heteroaromatic units at precisely defined positions in the conjugated backbone, which would be valuable for tuning their optical, electronic and magnetic properties. Here we report the solution-phase synthesis of a porphyrin-fused graphene nanoribbon (PGNR). This PGNR has metalloporphyrins fused into a twisted fjord-edged GNR backbone; it consists of long chains (>100 nm), with a narrow optical bandgap (~1.0 eV) and high local charge mobility (>400 cm2 V-1 s-1 by terahertz spectroscopy). We use this PGNR to fabricate ambipolar field-effect transistors with appealing switching behaviour, and single-electron transistors displaying multiple Coulomb diamonds. These results open an avenue to π-extended nanostructures with engineerable electrical and magnetic properties by transposing the coordination chemistry of porphyrins into graphene nanoribbons.

A Novel Leadership Curriculum for Emergency Medicine Residents.

Audience and Type of Curriculum: This longitudinal leadership curriculum is designed for emergency medicine residents at all levels, with individual sessions designed for each residency year. Length of Curriculum: This curriculum runs once annually over three to four years of emergency medicine residency. Introduction: Leadership is a vital skill for emergency physicians but is often passively taught during residency training. Strong leadership skills can lead to improved patient outcomes, but very few residency programs in any specialty and no emergency medicine residency programs have published comprehensive leadership training curricula. Educational Goals: The goals of this curriculum are to expose Emergency Medicine residents to the basics of leadership, to provide a graduated series of interactive, psychologically safe environments to explore individual leadership styles, to review interesting relevant literature, and to discuss leadership principles and experiences with senior leaders in our Emergency Department. Educational Methods: The educational strategies used in this curriculum include: brief lecture-style seminars, small group discussion and reflection, and a panel-style discussion. Research Methods: The educational content of this curriculum was evaluated by learners via feedback surveys after each session. Results: Course evaluations conducted in both 2017 and 2020 showed that more than 89% of resident participants found these sessions "useful" or "very useful." All residents surveyed agreed that leadership is an important topic for emergency medicine residency, and 76% felt that the inclusion of leadership content strengthened the residency's curriculum. Suggestions for future topics included handling personal conflict and discussing transitions in leadership during yearly residency promotions. Discussion: The curriculum has been successfully implemented for seven years. It has proven to be sustainable and requires minimal resources. The residents report high satisfaction with the curriculum and agree that formal instruction on the topic of leadership is important to their on-shift performance and careers. Topics: Leadership, communication.

Template-Directed Synthesis of Strained meso-meso-Linked Porphyrin Nanorings.

Strained macrocycles display interesting properties, such as conformational rigidity, often resulting in enhanced π-conjugation or enhanced affinity for non-covalent guest binding, yet they can be difficult to synthesize. Here we use computational modeling to design a template to direct the formation of an 18-porphyrin nanoring with direct meso-meso bonds between the porphyrin units. Coupling of a linear 18-porphyrin oligomer in the presence of this template gives the target nanoring, together with an unexpected 36-porphyrin ring by-product. Scanning tunneling microscopy (STM) revealed the elliptical conformations and flexibility of these nanorings on a Au(111) surface.

Wafer-Scale Two-Dimensional Semiconductors for Deep UV Sensing.

2D semiconductors (2SEM) can transform many sectors, from information and communication technology to healthcare. To date, top-down approaches to their fabrication, such as exfoliation of bulk crystals by "scotch-tape," are widely used, but have limited prospects for precise engineering of functionalities and scalability. Here, a bottom-up technique based on epitaxy is used to demonstrate high-quality, wafer-scale 2SEM based on the wide band gap gallium selenide (GaSe) compound. GaSe layers of well-defined thickness are developed using a bespoke facility for the epitaxial growth and in situ studies of 2SEM. The dominant centrosymmetry and stacking of the individual van der Waals layers are verified by theory and experiment; their optical anisotropy and resonant absorption in the UV spectrum are exploited for photon sensing in the technological UV-C spectral range, offering a scalable route to deep-UV optoelectronics.

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.

Lithium Iron Phosphate/Carbon (LFP/C) Composite Using Nanocellulose as a Reducing Agent and Carbon Source.

Lithium iron phosphate (LiFePO4, LFP) is the most promising cathode material for use in safe electric vehicles (EVs), due to its long cycle stability, low cost, and low toxicity, but it suffers from low conductivity and ion diffusion. In this work, we present a simple method to obtain LFP/carbon (LFP/C) composites with different types of NC: cellulose nanocrystal (CNC) and cellulose nanofiber (CNF). Microwave-assisted hydrothermal synthesis was used to obtain LFP with nanocellulose inside the vessel, and the final LFP/C composite was achieved by heating the mixture under a N2 atmosphere. The resulting LFP/C indicated that the NC in the reaction medium not only acts as the reducing agent that aqueous iron solutions need (avoiding the use of other chemicals), but also as a stabiliser of the nanoparticles produced in the hydrothermal synthesis, obtaining fewer agglomerated particles compared to synthesis without NC. The sample with the best coating-and, therefore, the best electrochemical response-was the sample with 12.6% carbon derived from CNF in the composite instead of CNC, due to its homogeneous coating. The utilisation of CNF in the reaction medium could be a promising method to obtain LFP/C in a simple, rapid, and low-cost way, avoiding the waste of unnecessary chemicals.

Covalent Template-Directed Synthesis of a Spoked 18-Porphyrin Nanoring.

Rings of porphyrins mimic natural light-harvesting chlorophyll arrays and offer insights into electronic delocalization, providing a motivation for creating larger nanorings with closely spaced porphyrin units. Here, we demonstrate the first synthesis of a macrocycle consisting entirely of 5,15-linked porphyrins. This porphyrin octadecamer was constructed using a covalent six-armed template, made by cobalt-catalyzed cyclotrimerization of an H-shaped tolan with porphyrin trimer ends. The porphyrins around the circumference of the nanoring were linked together by intramolecular oxidative meso-meso coupling and partial ß-ß fusion, to give a nanoring consisting of six edge-fused zinc(II) porphyrin dimer units and six un-fused nickel(II) porphyrins. STM imaging on a gold surface confirms the size and shape of the spoked 18-porphyrin nanoring (calculated diameter: 4.7 nm).

Bimetallic NiPt nanoparticles-enhanced catalyst supported on alginate-based biohydrogels for sustainable hydrogen production.

Alginate hydrogel beads were loaded with bimetallic NiPt nanoparticles by in situ reduction of the respective polymer matrix containing precursor metallic ions using a NaBH4 aqueous solution. The alginate hydrogel beads loaded with NiPt nanoparticles were characterized by TEM, AAS, FT-IR, TGA, XPS, and oscillatory rheometry. The prepared hybrid hydrogels were proven to be effective as catalytic materials for the hydrolysis of ammonia borane (AB) for quantitative hydrogen generation using catalytic loadings of 0.1 mol%. In addition, the reaction mechanism of the hydrolytic reaction using NiPt loaded alginate hydrogel beads was determined by Langmuir-Hinshelwood model. The experimental results showed that the reaction mechanism consisted of an initial fast adsorption of reactants at the surface of the nanoparticles, followed by a rate-limiting surface reaction. The NiPt nanoalloys exhibited an enhanced behavior for hydrogen generation with a maximum TOF of 84.1 min-1, almost 71 % higher compared to monometallic platinum atoms, and likely related to a synergistic interaction between both metals. Finally, the hydrogel matrix enabled the material to be easily recovered from the reaction medium and reused in further catalytic cycles without desorption of active nanoparticles from the material.

Bending a photonic wire into a ring.

Natural light-harvesting systems absorb sunlight and transfer its energy to the reaction centre, where it is used for photosynthesis. Synthetic chromophore arrays provide useful models for understanding energy migration in these systems. Research has focused on mimicking rings of chlorophyll molecules found in purple bacteria, known as 'light-harvesting system 2'. Linear meso-meso linked porphyrin chains mediate rapid energy migration, but until now it has not been possible to bend them into rings. Here we show that oligo-pyridyl templates can be used to bend these rod-like photonic wires to create covalent nanorings that consist of 24 porphyrin units and a single butadiyne link. Their elliptical conformations have been probed by scanning tunnelling microscopy. This system exhibits two excited state energy transfer processes: one from a bound template to the peripheral porphyrins and one, in the template-free ring, from the exciton-coupled porphyrin array to the π-conjugated butadiyne-linked porphyrin dimer segment.

A soft x-ray probe of a titania photoelectrode sensitized with a triphenylamine dye.

We present a thorough soft x-ray photoelectron spectroscopy (XPS) study of a mesoporous titanium dioxide electrode sensitized with the dye 4-(diphenylamino)phenylcyanoacrylic acid, referred to as "L0." Supported by calculations, the suite of XPS, x-ray absorption spectroscopy, and resonant photoelectron spectroscopy allows us to examine bonding interactions between the dye and the surface and the frontier electronic structure at the molecule-oxide interface. While placing these measurements in the context of existing literature, this paper is intended as a useful reference for further studies of more complex triphenylamine based sensitizers.

"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).

Resonant inelastic X-ray scattering of a Ru photosensitizer: Insights from individual ligands to the electronic structure of the complete molecule.

N 1s Resonant Inelastic X-ray Scattering (RIXS) was used to probe the molecular electronic structure of the ruthenium photosensitizer complex cis-bis(isothiocyanato) bis(2,2'-bipyridyl-4,4'-dicarboxylato) ruthenium(II), known as "N3." In order to interpret these data, crystalline powder samples of the bipyridine-dicarboxylic acid ligand ("bi-isonicotinic acid") and the single ring analog "isonicotinic acid" were studied separately using the same method. Clear evidence for intermolecular hydrogen bonding is observed for each of these crystalline powders, along with clear vibronic coupling features. For bi-isonicotinic acid, these results are compared to those of a physisorbed multilayer, where no hydrogen bonding is observed. The RIXS of the "N3" dye, again prepared as a bulk powder sample, is interpreted in terms of the orbital contributions of the bi-isonicotinic acid and thiocyanate ligands by considering the two different nitrogen species. This allows direct comparison with the isolated ligand molecules where we highlight the impact of the central Ru atom on the electronic structure of the ligand. Further interpretation is provided through complementary resonant photoemission spectroscopy and density functional theory calculations. This combination of techniques allows us to confirm the localization and relative coupling of the frontier orbitals and associated vibrational losses.

Hybrid light emitting diodes based on stable, high brightness all-inorganic CsPbI3 perovskite nanocrystals and InGaN.

Despite important advances in the synthesis of inorganic perovskite nanocrystals (NCs), the long-term instability and degradation of their quantum yield (QY) over time need to be addressed to enable the further development and exploitation of these nanomaterials. Here we report stable CsPbI3 perovskite NCs and their use in hybrid light emitting diodes (LEDs), which combine in one system the NCs and a blue GaN-based LED. Nanocrystals with improved morphological and optical properties are obtained by optimizing the post-synthesis replacement of oleic acid ligands with iminodibenzoic acid: the NCs have a long shelf-life (>2 months), stability under different environmental conditions, and a high QY, of up to 90%, in the visible spectral range. Ligand replacement enables the engineering of the morphological and optical properties of the NCs. Furthermore, the NCs can be used to coat the surface of a GaN-LED to realize a stable diode where they are excited by blue light from the LED under low current injection conditions, resulting in emissions at distinct wavelengths in the visible range. The high QY and fluorescence lifetime in the nanosecond range are key parameters for visible light communication, an emerging technology that requires high-performance visible light sources for secure, fast energy-efficient wireless transmission.

The dermal skeleton of the jawless vertebrate Tremataspis mammillata (Osteostraci, stem-Gnathostomata).

Osteostracans are the closest jawless relatives of jawed vertebrates, informing the gradual assembly of the vertebrate mineralised skeleton. Conflicting interpretations of their dermal skeletal histology arise from failure to account for topological variation, obscuring their significance in elucidating vertebrate skeletal evolution. To resolve this, we characterize the cranial and trunk dermal skeleton of a single individual of Tremataspis mammillata (Osteostraci, Thyestiida) at submicron resolution using synchrotron- and computed- tomography. Our results show that the architecture of the Tremataspis dermal skeleton is, for the most part, conserved over the skeleton and is broadly consistent with previous histological hypotheses based on 2D thin section study. We resolve debate over the homology of the basal layer, identifying it as osteogenic acellular isopedin rather than odontogenic elasmodine or metaplastic ossification of the stratum compactum of the dermis. We find topological variation between all dermal skeletal elements studied, and particularly between the cranial and postcranial dermal skeleton. This variation can be largely explained by reduction in differentiation due to geometric constraints imposed within smaller skeletal elements, such as scales. Our description of the dermal skeleton of Tremataspis mammillata provides a foundation for interpreting data from cursory topological samples of dermal skeletal diversity obtained in other osteostracans. This reveals general aspects of histological structure that must be ancestral for osteostracans and, likely, ancestral jawed vertebrates. Finally, we draw the distinction between hypotheses and descriptions in palaeohistology.

Direct Synthesis of Multiplexed Metal-Nanowire-Based Devices by Using Carbon Nanotubes as Vector Templates.

We present the synthesis of metal nanowires in a multiplexed device configuration using single-walled carbon nanotubes (SWNTs) as nanoscale vector templates. The SWNT templates control the dimensionality of the wires, allowing precise control of their size, shape, and orientation; moreover, a solution-processable approach enables their linear deposition between specific electrode pairs in electronic devices. Electrical characterization demonstrated the successful fabrication of metal nanowire electronic devices, while multiscale characterization of the different fabrication steps revealed details of the structure and charge transfer between the material encapsulated and the carbon nanotube. Overall the strategy presented allows facile, low-cost, and direct synthesis of multiplexed metal nanowire devices for nanoelectronic applications.

In situ XPS analysis of the atomic layer deposition of aluminium oxide on titanium dioxide.

Ultra-thin aluminium oxide was grown on a rutile titanium dioxide surface by atomic layer deposition using trimethylaluminium and water precursors. This process, carried out using realistic temperatures and pressures (1 mbar, 450 K), was monitored in situ using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). This provides insight into the surface chemistry at the interface between the two oxide layers - specifically the reduction of titanium atoms from Ti4+ to Ti3+ upon dosing of trimethylaluminium. These defect states become locked into the heterojunction's interface, with implications to its electronic structure, and can act as an indicator as to when complete coverage of the rutile substrate is achieved.

Ultra-fast intramolecular vibronic coupling revealed by RIXS and RPES maps of an aromatic adsorbate on TiO2(110).

Two-dimensional resonant inelastic x-ray scattering (RIXS) and resonant photoelectron spectroscopy (RPES) maps are presented for multilayer and monolayer coverages of an aromatic molecule (bi-isonicotinic acid) on the rutile TiO2(110) single crystal surface. The data reveal ultra-fast intramolecular vibronic coupling upon core excitation from the N 1s orbital into the lowest unoccupied molecular orbital (LUMO) derived resonance. In the RIXS measurements, this results in the splitting of the participator decay channel into a purely elastic line which disperses linearly with excitation energy and a vibronic coupling channel at constant emission energy. In the RPES measurements, the vibronic coupling results in a linear shift in binding energy of the participator channel as the excitation is tuned over the LUMO-derived resonance. Localisation of the vibrations on the molecule on the femtosecond time scale results in predominantly inelastic scattering from the core-excited state in both the physisorbed multilayer and the chemisorbed monolayer.

Exploring ultra-fast charge transfer and vibronic coupling with N 1s RIXS maps of an aromatic molecule coupled to a semiconductor.

We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer bi-isonicotinic acid adsorbed on the rutile TiO2(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveal ultra-fast intramolecular vibronic coupling, particularly during excitation into the lowest unoccupied molecular orbital-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule coupled to a wide bandgap semiconductor to be considered in the same way as the core-hole clock implementation of resonant photoemission spectroscopy (RPES). However, contrary to RPES measurements, we find no evidence for the depletion of the participator channel under the conditions of ultra-fast charge transfer from the molecule to the substrate densities of states, on the time scale of the core-hole lifetime. These results suggest that the radiative core-hole decay processes in RIXS are not significantly modified by charge transfer on the femtosecond time scale in this system.