Multifunctional Buried Interface Modification Enables Efficient Tin Perovskite Solar Cells.

Tin perovskite solar cells (PSCs) are considered promising candidates to promote lead-free perovskite photovoltaics. However, their power conversion efficiency (PCE) is limited by the easy oxidation of Sn2+ and low quality of tin perovskite film. Herein, an ultra-thin 1-carboxymethyl-3-methylimidazolium chloride (ImAcCl) layer is used to modify the buried interface in tin PSCs, which can induce multifunctional improvements and remarkably enhance the PCE. The carboxylate group (CO) and the hydrogen bond donor (NH) in ImAcCl can interact with tin perovskites, thus significantly suppressing the oxidation of Sn2+ and reducing the trap density in perovskite films. The interfacial roughness is reduced, which contributes to a high-quality tin perovskite film with increased crystallinity and compactness. In addition, the buried interface modification can modulate the crystal dimensionality, favoring the formation of large bulk-like crystals instead of low-dimensional ones in tin perovskite films. Therefore, the charge carrier transport is effectively promoted and the charge carrier recombination is suppressed. Eventually, tin PSCs show a remarkably enhanced PCE from 10.12% to 12.08%. This work highlights the importance of buried interface engineering and provides an effective way to realize efficient tin PSCs.

Self-Assembly of Polymer-Modified FePt Magnetic Nanoparticles and Block Copolymers.

The fabrication of nanocomposites containing magnetic nanoparticles is gaining interest as a model for application in small electronic devices. The self-assembly of block copolymers (BCPs) makes these materials ideal for use as a soft matrix to support the structural ordering of the nanoparticles. In this work, a high-molecular-weight polystyrene-b-poly(methyl methacrylate) block copolymer (PS-b-PMMA) was synthesized through anionic polymerization. The influence of the addition of different ratios of PMMA-coated FePt nanoparticles (NPs) on the self-assembled morphology was investigated using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The self-assembly of the NPs inside the PMMA phase at low particle concentrations was analyzed statistically, and the negative effect of higher particle ratios on the lamellar BCP morphology became visible. The placement of the NPs inside the PMMA phase was also compared to theoretical descriptions. The magnetic addressability of the FePt nanoparticles inside the nanocomposite films was finally analyzed using bimodal magnetic force microscopy and proved the magnetic nature of the nanoparticles inside the microphase-separated BCP films.

Revealing Surface and Interface Evolution of Molybdenum Nitride as Carrier-Selective Contacts for Crystalline Silicon Solar Cells.

Molybdenum nitride (MoNx) was perceived as carrier-selective contacts (CSCs) for crystalline silicon (c-Si) solar cells due to having proper work functions and excellent conductivities. However, the poor passivation and non-Ohmic contact at the c-Si/MoNx interface endow an inferior hole selectivity. Here, the surface, interface, and bulk structures of MoNx films are systematically investigated by X-ray scattering, surface spectroscopy, and electron microscope analysis to reveal the carrier-selective features. Surface layers with the composition of MoO2.51N0.21 form upon air exposure, which induces the overestimated work function and explains the origin of inferior hole selectivities. The c-Si/MoNx interface is confirmed to adopt long-term stability, providing guidance for designing stable CSCs. A detailed evolution of the scattering length density, domain sizes, and crystallinity in the bulk phase is presented to elucidate its superior conductivity. These multiscale structural investigations offer a clear structure-function correlation of MoNx films, providing key inspiration for developing excellent CSCs for c-Si solar cells.

Endovascular Repair of Iatrogenic Inferior Vena Cava and Iliac Vein Injury: A Case Series and Review of the Literature.

OBJECTIVE: Iatrogenic injury to the large abdominopelvic veins can he highly morbid, and open surgical repair is technically challenging. Endovascular repair with covered stenting across the injured segment offers an alternative to open surgical management. We present a series of patients with operative injury to the inferior vena cava (IVC) and iliac veins who were treated utilizing an endovascular approach and review the available literature on this technique. METHODS: A PubMed keyword and MeSH term search was performed, and titles were reviewed for relevance by the first author. Studies related to endovascular repair of iatrogenic injury to the IVC and iliac veins were then read in detail for possible inclusion in the review. Those deemed appropriate were further analyzed for interventional approach, stent type and size, technical success, post-procedural pharmacologic management, complications and surveillance strategy. RESULTS: The initial search resulted in 6221 publications. A total of 17 met criteria for inclusion, all of which were case reports or series. Twenty-six patients were described as suffering iatrogenic injury to the IVC or iliac veins, treated with various types and sizes of stents. All cases achieved technical success with hemorrhage control. Procedural complications occurred in 15.4% of cases, including 3 cases of acute thrombus formation and 1 case of stenosis caudal to the initial stent edge requiring additional stenting. Two additional patients experienced stent occlusion in the surveillance period. CONCLUSIONS: Endovascular repair of iatrogenic injury to the IVC and iliac veins can be an effective management option. However, due to limited data regarding this approach, many technical questions remain, including ideal size and type of stent graft, necessity and duration of post-procedural anticoagulant or antiplatelet therapy and appropriate surveillance. Additionally, long term outcomes in this population have not yet been described.

Angiotensin II Use in Treatment of Refractory Shock Due to Benazepril and Amlodipine Toxic Ingestion.

INTRODUCTION: Calcium channel blockers (CCB) are a leading cause of ingestion-associated fatality. Angiotensin-converting enzyme inhibitor (ACEi) overdose as part of co-ingestion is common and associated with refractory shock. Treatment options to manage this profound vasoplegia are limited. We describe the first case of use of newly formulated Angiotensin II for treatment of severe ACEi and CCB poisoning. CASE REPORT: A 57-year-old man presented after suicide attempt by ingesting 20 tablets each of amlodipine 10 mg and benazepril 20 mg. His hypotension was initially managed with 35 mL/kg of crystalloid, norepinephrine, and hyperinsulinemic euglycemic therapy (HIET). His hemodynamics further deteriorated, and he developed lactic acidosis, electrolyte derangements, and renal dysfunction. Further complications of his ingestion included cardiac arrest, subsequent requirement for emergency cricothyrotomy, and renal replacement therapy. Maximal hemodynamic support with HIET therapy insulin drip 4.4 units/kg/hour, norepinephrine 2 mcg/kg/min, epinephrine 1 mcg/kg/min, vasopressin .06 units/hour, and intravenous lipid emulsion was unsuccessful. Ang II was started and titrated to maximal doses with dramatic improvement in hemodynamics. Within hours of starting Ang II, epinephrine was stopped and norepinephrine decreased by 50%. He was downgraded from the intensive care unit without any ongoing end-organ dysfunction. DISCUSSION: Isolated CCB overdoses have high complication rates and well-established treatments. Therefore, management of CCB and ACEi co-ingestion is typically driven by CCB poisoning algorithm. There are multiple reports of CCB and ACEi co-ingestions causing treatment-refractory shock. Therapeutic options are limited by toxicities and availability of salvage therapies. Ang II is a safe and highly effective option to manage these patients.

Elastic Behavior of Nb2O5/Al2O3 Core-Shell Nanowires in Terms of Short-Range-Order Structures.

Single-crystalline niobium pentoxide nanowires (NWs) of length 10-15 µm and diameter 100-200 nm are synthesized by thermal oxidation of niobium substrates in a mild vacuum (3-10 mbar). Amorphous Al2O3 shells of varying thicknesses (10, 30, 40, and 50 nm) are deposited on top of the wires using atomic layer deposition. Bending tests of the uncoated Nb2O5 NWs and the Nb2O5/Al2O3 core-shell NWs are carried out inside a scanning electron microscope using a micromanipulator with a force measurement tip. The experimental deflection curves are modeled with Euler-Bernoulli (E-B) beam theory, and the Young's modulus is manipulated to determine the best fit. The Nb2O5 NWs with no shell are determined to have a Young's modulus of 67 ± 10 GPa, which agrees with the published data on Nb2O5 thin films. For core-shell NWs, only small deflections of the wires with 10 and 30 nm thick shells can be fitted with the E-B model when utilizing constant Young's modulus values of 67 GPa for the Nb2O5 core and about 160 GPa for the Al2O3 shell. When allowing for a change in the Young's modulus of the Al2O3 shell, the Young's modulus is determined to be at 120 ± 10 GPa for 10 nm and 145 ± 12 GPa for 30 nm at the highest applied load. For thicknesses of 40 nm and 50 nm, we observed a reduced but constant 120 ± 11 and 111 ± 10 GPa, respectively. Such behavior may result from structural disordering of the amorphous Al2O3 through reducing fractions of the densely packed polyhedra, while the fractions of the loosely packed polyhedra increase as a result of the increasing strain or the fabrication process. The increased disorder is associated with increased average interatomic spacing. Thus, the atomic bonding force and also the Young's modulus decrease.

Establishing Consensus-based Objectives for the Creation of an Opioid Overdose Curriculum for Emergency Medical Services Clinicians.

OBJECTIVES: Emergency medical services (EMS) clinicians are on the front lines of the opioid epidemic and are often the first health care personnel system to contact patients experiencing opioid toxicity. Although national educational guidelines include opioid toxicity, no specific standardized prehospital educational objectives or competencies exist. The goal of this project was to identify objectives for an EMS opioid toxicity curriculum that could be used for EMS training. METHODS: A list of preliminary educational objectives from U.S. EMS training programs was compiled and reviewed by a group of experts. The Delphi method was used to attain consensus on a final list of objectives for an EMS opioid curriculum. RESULTS: A total of 107 opioid-related preliminary objectives were identified and then narrowed down to 81 preliminary objectives after accounting for redundancy. After four successive rounds of evaluating/accepting/rejecting objectives, 18 final objectives were identified and unanimously approved by the expert panel. CONCLUSION: We identified 18 objectives to serve as a framework for an opioid toxicity curriculum for EMS clinicians. These objectives can serve as a basis for creating a standardized didactic training program for EMS training programs nationwide. Further evaluation will be needed to explore the best means for educational program delivery.

Beyond linearity: bent crystalline copper nanowires in the small-to-moderate regime.

Several models can describe the nonlinear response of 1D objects to bending under a concentrated load. Successive stages consisting of geometrical and, additionally, mechanical non-linearity can be identified in moderately large extensions. We provide an explicit bending moment function with terms accounting for the linearity (Euler-Bernoulli), quasi-linearity, geometrical and finally, mechanical non-linearity as global features of a moderately large elastic deformation. We apply our method, also suitable for other metals, to the experimental data of Cu nanowires (NWs) with an aspect ratio of about 16 under different concentrated loadings. The spatial distribution of strain-hardening/softening along the wire or through the cross-section is also demonstrated. As a constitutive parameter, the strain-dependent stretch modulus represents, undoubtedly, changes in the material properties as the deformation progresses. At the highest load, the Green-Lagrange strain reaches a 12.5% extension with a corresponding ultra-high strength of about 7.45 GPa at the most strained volume still in the elastic regime. The determined stretch modulus indicates a significantly lower elastic response with an approximated Young's modulus (E ≅ 65 GPa) and a third-order elastic constant, C 111 ≅ -350 GPa. Surprisingly, these constants suggest a 25-35% of that of the bulk counterparts. Ultimately, the method not only provides a quantitative description of the bent Cu NWs, but also indicates the robustness of the theory of nonlinear elasticity.

Nonlinear elastic aspects of multi-component iron oxide core-shell nanowires by means of atom probe tomography, analytical microscopy, and nonlinear mechanics.

One-dimensional objects as nanowires have been proven to be building blocks in novel applications due to their unique functionalities. In the realm of magnetic materials, iron-oxides form an important class by providing potential solutions in catalysis, magnetic devices, drug delivery, or in the field of sensors. The accurate composition and spatial structure analysis are crucial to describe the mechanical aspects and optimize strategies for the design of multi-component NWs. Atom probe tomography offers a unique analytic characterization tool to map the (re-)distribution of the constituents leading to a deeper insight into NW growth, thermally-assisted kinetics, and related mechanisms. As NW-based devices critically rely on the mechanical properties of NWs, the appropriate mechanical modeling with the resulting material constants is also highly demanded and can open novel ways to potential applications. Here, we report a compositional and structural study of quasi-ceramic one-dimensional objects: α-Fe ⊕ α-FeOOH(goethite) ⊕ Pt and α-Fe ⊕ α-Fe3O4(magnetite) ⊕ Pt core-shell NWs. We provide a theoretical model for the elastic behavior with terms accounting for the geometrical and mechanical nonlinearity, prior and subsequent to thermal treatment. The as-deposited system with a homogeneous distribution of the constituents demonstrates strikingly different structural and elastic features than that of after annealing, as observed by applying atom probe tomography, energy-dispersive spectroscopy, analytic electron microscopy, and a micromanipulator nanoprobe system. During annealing at a temperature of 350 °C for 20 h, (i) compositional partitioning between phases (α-Fe, α-Fe3O4 and in a minority of α-Fe2O3) in diffusional solid-solid phase transformations takes place, (ii) a distinct newly-formed shell formation develops, (iii) the degree of crystallinity increases and (iv) nanosized precipitation of evolving phases is detected leading to a considerable change in the description of the elastic material properties. The as-deposited nanowires already exhibit a significantly large maximum strain (1-8%) and stress (3-13 GPa) in moderately large bending tests, which become even more enhanced after the annealing treatment resulting at a maximum of about 2.5-10.5% and 6-18 GPa, respectively. As a constitutive parameter, the strain-dependent stretch modulus undoubtedly represents changes in the material properties as the deformation progresses.

Sustained presentation of BMP-2 enhances osteogenic differentiation of human adipose-derived stem cells in gelatin hydrogels.

Human adipose-derived stem cells (hASCs) show great potential for healing bone defects. Bone morphogenetic protein-2 (BMP-2) has been reported to stimulate their osteogenic differentiation both in vitro and in vivo. Here, methacrylated gelatin (GelMA) hydrogels were evaluated as a system to deliver BMP-2 to encapsulated hASCs from two different donors, and BMP-2 delivered from the hydrogels was compared to BMP-2 presented exogenously in culture media. GelMA hydrogels were shown to provide sustained, localized presentation of BMP-2 due to electrostatic interactions between the growth factor and biomaterial after an initial burst release. Both donors exhibited similar responses to the loaded and exogenous growth factor; BMP-2 from the hydrogels had a statistically significant effect on hASC osteogenic differentiation compared to exogenous BMP-2. Expression of alkaline phosphatase was accelerated, and cells in hydrogels with loaded BMP-2 deposited more calcium at one, two, and four weeks than cells without BMP-2 or with the growth factor presented in the media. There were no statistically significant differences in calcium content between groups with 25, 50, or 100 µg/mL loaded BMP-2, suggesting that using a lower growth factor dose may be as effective as a higher loading amount in this system. Taken together, these findings suggest that controlled delivery of BMP-2 from the GelMA enhances its osteogenic bioactivity compared to free growth factor presented in the media. Thus, the GelMA system is a promising biomaterial for BMP-2-mediated hASC osteogenesis. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 1387-1397, 2016.

Internal vacuum-assisted closure device in the swine model of severe liver injury.

OBJECTIVES: The authors present a novel approach to nonresectional therapy in major hepatic trauma utilizing intraabdominal perihepatic vacuum assisted closure (VAC) therapy in the porcine model of Grade V liver injury. METHODS: A Grade V injury was created in the right lobe of the liver in a healthy pig. A Pringle maneuver was applied (4.5 minutes total clamp time) and a vacuum assisted closure device was placed over the injured lobe and connected to suction. The device consisted of a perforated plastic bag placed over the liver, followed by a 15 cm by 15cm VAC sponge covered with a nonperforated plastic bag. The abdomen was closed temporarily. Blood loss, cardiopulmonary parameters and bladder pressures were measured over a one-hour period. The device was then removed and the animal was euthanized. RESULTS: Feasibility of device placement was demonstrated by maintenance of adequate vacuum suction pressures and seal. VAC placement presented no major technical challenges. Successful control of ongoing liver hemorrhage was achieved with the VAC. Total blood loss was 625 ml (20ml/kg). This corresponds to class II hemorrhagic shock in humans and compares favorably to previously reported estimated blood losses with similar grade liver injuries in the swine model. No post-injury cardiopulmonary compromise or elevated abdominal compartment pressures were encountered, while hepatic parenchymal perfusion was maintained. CONCLUSION: These data demonstrate the feasibility and utility of a perihepatic negative pressure device for the treatment of hemorrhage from severe liver injury in the porcine model.

General surgery resident attrition and the 80-hour workweek.

BACKGROUND: This study examines the effect of implementation of the resident duty-hour regulations on the attrition rate of general surgery residents. METHODS: A 7-part survey encompassing the 2001 to 2004 academic years was sent to program directors of general surgery residency programs in the United States. RESULTS: One hundred twenty-four of 252 programs (49%) responded, reporting a loss of 338 categorical residents. The total attrition rate increased from .6 residents lost/program/y to .8 residents/program/y (P = .0013). Lifestyle concerns were the most commonly reported reason for residents leaving during surgical training. The majority (56%) of those who left surgery entered other fields of medicine (ie, Anesthesia and Family Medicine most commonly). CONCLUSIONS: More residents are leaving general surgery training since the institution of the 80-hour workweek. Despite improvements in work hours and lifestyle during surgical training, residents migrate to specialties that are conducive to a more controllable lifestyle after experiencing surgery residency.

Wnt-4 activates the canonical beta-catenin-mediated Wnt pathway and binds Frizzled-6 CRD: functional implications of Wnt/beta-catenin activity in kidney epithelial cells.

The Wnt signaling pathway is central to the development of all animals and to cancer progression, yet largely unknown are the pairings of secreted Wnt ligands to their respective Frizzled transmembrane receptors or, in many cases, the relative contributions of canonical (beta-catenin/LEF/TCF) versus noncanonical Wnt signals. Specifically, in the kidney where Wnt-4 is essential for the mesenchymal to epithelial transition that generates the tissue's collecting tubules, the corresponding Frizzled receptor(s) and downstream signaling mechanism(s) are unclear. In this report, we addressed these issues using Madin-Darby Canine Kidney (MDCK) cells, which are competent to form tubules in vitro. Employing established reporter constructs of canonical Wnt/beta-catenin pathway activity, we have determined that MDCK cells are highly responsive to Wnt-4, -1, and -3A, but not to Wnt-5A and control conditions, precisely reflecting functional findings from Wnt-4 null kidney mesenchyme ex vivo rescue studies. We have confirmed that Wnt-4's canonical signaling activity in MDCK cells is mediated by downstream effectors of the Wnt/beta-catenin pathway using beta-Engrailed and dnTCF-4 constructs that suppress this pathway. We have further found that MDCK cells express the Frizzled-6 receptor and that Wnt-4 forms a biochemical complex with the Frizzled-6 CRD. Since Frizzled-6 did not appear to transduce Wnt-4's canonical signal, data supported recently by Golan et al., there presumably exists another as yet unknown Frizzled receptor(s) mediating Wnt-4 activation of beta-catenin/LEF/TCF. Finally, we report that canonical Wnt/beta-catenin signals cells help maintain cell growth and survival in MDCK cells but do not contribute to standard HGF-induced (nonphysiologic) tubule formation. Our results in combination with work from Xenopus laevis (not shown) lead us to believe that Wnt-4 binds both canonical and noncanonical Frizzled receptors, thereby activating Wnt signaling pathways that may each contribute to kidney tubulogenesis.

The import of phosphoenolpyruvate by plastids from developing embryos of oilseed rape, Brassica napus (L.), and its potential as a substrate for fatty acid synthesis.

The plastidial phosphoenolpyruvate (PEP)/phosphate translocator (PPT) is expressed in the developing embryos of oilseed rape (Brassica napus L.). PEP can be imported by plastids isolated from embryos and used for fatty acid synthesis at rates that are sufficient to account for one-third of the rate of fatty acid synthesis in vivo. This provides the first experimental evidence for uptake of PEP and incorporation of carbon from it into fatty acids by plastids. PEP metabolism in isolated plastids is able to provide some of the ATP required for fatty acid synthesis. Expression of the PPT and related glucose 6-phosphate (Glc-6-P) translocator (GPT) is high in early embryo and leaf development and then declines. The marked decline in the abundance of PPT and GPT transcripts between the pre- and mid-oil accumulating stages of embryo development in B. napus does not correlate with the corresponding translocator activities, which both increase over the same period. This means that transcript abundance cannot be used to infer the activity of the translocators.

DNA triplet repeats mediate heterochromatin-protein-1-sensitive variegated gene silencing.

Gene repression is crucial to the maintenance of differentiated cell types in multicellular organisms, whereas aberrant silencing can lead to disease. The organization of DNA into chromatin and heterochromatin is implicated in gene silencing. In chromatin, DNA wraps around histones, creating nucleosomes. Further condensation of chromatin, associated with large blocks of repetitive DNA sequences, is known as heterochromatin. Position effect variegation (PEV) occurs when a gene is located abnormally close to heterochromatin, silencing the affected gene in a proportion of cells. Here we show that the relatively short triplet-repeat expansions found in myotonic dystrophy and Friedreich's ataxia confer variegation of expression on a linked transgene in mice. Silencing was correlated with a decrease in promoter accessibility and was enhanced by the classical PEV modifier heterochromatin protein 1 (HP1). Notably, triplet-repeat-associated variegation was not restricted to classical heterochromatic regions but occurred irrespective of chromosomal location. Because the phenomenon described here shares important features with PEV, the mechanisms underlying heterochromatin-mediated silencing might have a role in gene regulation at many sites throughout the mammalian genome and modulate the extent of gene silencing and hence severity in several triplet-repeat diseases.