A Facile Molecular Approach to Amorphous Nickel Pnictides and Their Reconstruction to Crystalline Potassium-Intercalated γ-NiOOHx Enabling High-Performance Electrocatalytic Water Oxidation and Selective Oxidation of 5-Hydroxymethylfurfural.

The low-temperature molecular precursor approach can be beneficial to conventional solid-state methods, which require high temperatures and lead to relatively large crystalline particles. Herein, a novel, single-step, room-temperature preparation of amorphous nickel pnictide (NiE; EP, As) nanomaterials is reported, starting from NaOCE(dioxane)n and NiBr2 (thf)1.5 . During application for the oxygen evolution reaction (OER), the pnictide anions leach, and both materials fully reconstruct into nickel(III/IV) oxide phases (similar to γ-NiOOH) comprising edge-sharing (NiO6 ) layers with intercalated potassium ions and a d-spacing of 7.27 Å. Remarkably, the intercalated γ-NiOOHx phases are nanocrystalline, unlike the amorphous nickel pnictide precatalysts. This unconventional reconstruction is fast and complete, which is ascribed to the amorphous nature of the nanostructured NiE precatalysts. The obtained γ-NiOOHx can effectively catalyse the OER for 100 h at a high current density (400 mA cm-2 ) and achieves outstandingly high current densities (>600 mA cm-2 ) for the selective, value-added oxidation of 5-hydroxymethylfurfural (HMF). The NiP-derived γ-NiOOHx shows a higher activity for both processes due to more available active sites. It is anticipated that the herein developed, effective, room-temperature molecular synthesis of amorphous nickel pnictide nanomaterials can be applied to other functional transition-metal pnictides.

Combination of Highly Efficient Electrocatalytic Water Oxidation with Selective Oxygenation of Organic Substrates using Manganese Borophosphates.

One of the key catalytic reactions for life on earth, the oxidation of water to molecular oxygen, occurs in the oxygen-evolving complex of the photosystem II (PSII) mediated by a manganese-containing cluster. Considerable efforts in this research area embrace the development of efficient artificial manganese-based catalysts for the oxygen evolution reaction (OER). Using artificial OER catalysts for selective oxygenation of organic substrates to produce value-added chemicals is a worthwhile objective. However, unsatisfying catalytic performance and poor stability have been a fundamental bottleneck in the field of artificial PSII analogs. Herein, for the first time, a manganese-based anode material is developed and paired up for combining electrocatalytic water oxidation and selective oxygenations of organics delivering the highest efficiency reported to date. This can be achieved by employing helical manganese borophosphates, representing a new class of materials. The uniquely high catalytic activity and durability (over 5 months) of the latter precursors in alkaline media are attributed to its unexpected surface transformation into an amorphous MnOx phase with a birnessite-like short-range order and surface-stabilized MnIII sites under extended electrical bias, as unequivocally demonstrated by a combination of in situ Raman and quasi in situ X-ray absorption spectroscopy as well as ex situ methods.

Boosting Water Oxidation through In Situ Electroconversion of Manganese Gallide: An Intermetallic Precursor Approach.

For the first time, the manganese gallide (MnGa4 ) served as an intermetallic precursor, which upon in situ electroconversion in alkaline media produced high-performance and long-term-stable MnOx -based electrocatalysts for water oxidation. Unexpectedly, its electrocorrosion (with the concomitant loss of Ga) leads simultaneously to three crystalline types of MnOx minerals with distinct structures and induced defects: birnessite δ-MnO2 , feitknechtite ß-MnOOH, and hausmannite α-Mn3 O4 . The abundance and intrinsic stabilization of MnIII /MnIV active sites in the three MnOx phases explains the superior efficiency and durability of the system for electrocatalytic water oxidation. After electrophoretic deposition of the MnGa4 precursor on conductive nickel foam (NF), a low overpotential of 291 mV, comparable to that of precious-metal-based catalysts, could be achieved at a current density of 10 mA cm-2 with a durability of more than five days.

Boosting Electrocatalytic Hydrogen Evolution Activity with a NiPt3@NiS Heteronanostructure Evolved from a Molecular Nickel-Platinum Precursor.

A facile synthetic route to NiPt3@NiS heteronanostructures is reported, starting from a subsulfido bridged heterobimetallic nickel-platinum molecular precursor. Notably, the NiPt3@NiS on nickel foam displayed merely an overpotential of 12 mV at -10 mA cm-2, which is substantially lower than that of Pt or NiS, synthesized through a similar approach and represents the most active hydrogen evolution reaction (HER) electrocatalysts yet reported in alkaline solutions. NiPt3@NiS electrodes demonstrated an unceasing HER stability over 8 days, which is well over those reported for Pt-based catalysts signifying a capability of scaled hydrogen production.

Evolution of Superconductivity with Sr-Deficiency in Antiperovskite Oxide Sr3-xSnO.

Bulk superconductivity was recently reported in the antiperovskite oxide Sr3-xSnO, with a possibility of hosting topological superconductivity. We investigated the evolution of superconducting properties such as the transition temperature Tc and the size of the diamagnetic signal, as well as normal-state electronic and crystalline properties, with varying the nominal Sr deficiency x0. Polycrystalline Sr3-xSnO was obtained up to x0 = 0:6 with a small amount of SrO impurities. The amount of impurities increases for x0 > 0.6, suggesting phase instability for high deficiency. Mössbauer spectroscopy reveals an unusual Sn4- ionic state in both stoichiometric and deficient samples. By objectively analyzing superconducting diamagnetism data obtained from a large number of samples, we conclude that the optimal x0 lies in the range 0.5 < x0 < 0.6. In all superconducting samples, two superconducting phases appear concurrently that originate from Sr3-xSnO but with varying intensities. These results clarify the Sr deficiency dependence of the normal and superconducting properties of the antiperovskite oxide Sr3-xSnO will ignite future work on this class of materials.

Predictive and prognostic value of tumor volume and its changes during radical radiotherapy of stage III non-small cell lung cancer : A systematic review.

PURPOSE: Lung cancer remains the leading cause of cancer-related mortality worldwide. Stage III non-small cell lung cancer (NSCLC) includes heterogeneous presentation of the disease including lymph node involvement and large tumour volumes with infiltration of the mediastinum, heart or spine. In the treatment of stage III NSCLC an interdisciplinary approach including radiotherapy is considered standard of care with acceptable toxicity and improved clinical outcome concerning local control. Furthermore, gross tumour volume (GTV) changes during definitive radiotherapy would allow for adaptive replanning which offers normal tissue sparing and dose escalation. METHODS: A literature review was conducted to describe the predictive value of GTV changes during definitive radiotherapy especially focussing on overall survival. The literature search was conducted in a two-step review process using PubMed®/Medline® with the key words "stage III non-small cell lung cancer" and "radiotherapy" and "tumour volume" and "prognostic factors". RESULTS: After final consideration 17, 14 and 9 studies with a total of 2516, 784 and 639 patients on predictive impact of GTV, GTV changes and its impact on overall survival, respectively, for definitive radiotherapy for stage III NSCLC were included in this review. Initial GTV is an important prognostic factor for overall survival in several studies, but the time of evaluation and the value of histology need to be further investigated. GTV changes during RT differ widely, optimal timing for re-evaluation of GTV and their predictive value for prognosis needs to be clarified. The prognostic value of GTV changes is unclear due to varying study qualities, re-evaluation time and conflicting results. CONCLUSION: The main findings were that the clinical impact of GTV changes during definitive radiotherapy is still unclear due to heterogeneous study designs with varying quality. Several potential confounding variables were found and need to be considered for future studies to evaluate GTV changes during definitive radiotherapy with respect to treatment outcome.

Superconductivity in the antiperovskite Dirac-metal oxide Sr3-xSnO.

Investigations of perovskite oxides triggered by the discovery of high-temperature and unconventional superconductors have had crucial roles in stimulating and guiding the development of modern condensed-matter physics. Antiperovskite oxides are charge-inverted counterpart materials to perovskite oxides, with unusual negative ionic states of a constituent metal. No superconductivity was reported among the antiperovskite oxides so far. Here we present the first superconducting antiperovskite oxide Sr3-xSnO with the transition temperature of around 5 K. Sr3SnO possesses Dirac points in its electronic structure, and we propose from theoretical analysis a possibility of a topological odd-parity superconductivity analogous to the superfluid 3He-B in moderately hole-doped Sr3-xSnO. We envision that this discovery of a new class of oxide superconductors will lead to a rapid progress in physics and chemistry of antiperovskite oxides consisting of unusual metallic anions.

Surgical treatment of metastatic fractures of the femur: a retrospective analysis of 142 patients.

BACKGROUND: Pathologic fractures of long bones are common complications of the metastatic disease; however, the influence of the primary tumor, the stage of metastatic disease, different surgical techniques, and the postoperative mobility on the postoperative survival has not been clearly defined. The aim of this retrospective study was to evaluate outcome after surgical treatment for pathologic femur fractures. PATIENTS AND METHODS: A consecutive series of 142 patients with metastatic fractures of femur were retrospectively studied. The operative treatment was based on intramedullary fixation (n = 94), gliding screws (n = 15), other extramedullary fixation devices (n = 7), and arthroplasty (n = 23). RESULTS: Seventeen percent and 6% of the patients survived 1 year and 2 years, respectively, postoperatively. Postoperative survival was higher in patients with pathologic femur fractures because of breast carcinoma than in patients with other primary tumors. The rate of complications for patients with intramedullary stabilization, gliding screw fixation, and endoprosthetic replacement was 3.2%, 20%, and 8.6%, respectively. CONCLUSION: Although many studies describe the endoprosthetic replacement as the safer method to treat pathologic femur fractures, our data showed that intramedullary stabilization and endoprosthetic replacement to be safe, and equivalent alternatives to treat complete pathologic fractures of the femur in patients with advanced metastatic disease.

Surgical treatment of pathological fractures of the shaft of the humerus.

BACKGROUND: This report deals with the advantages and disadvantages associated with the most commonly used methods of stabilization after a pathologic fracture of the humerus shaft. PATIENTS: A total of 39 patients with 41 metastatic lesions and pathologic fractures of the humerus, treated surgically between 1992 and 2007, were retrospectively analyzed. RESULTS: The rate of local complications was 14.6% (6 of 41). Radial nerve injury was the only local complication and was exclusively observed in patients who underwent open reduction and plate fixation. The overall rate of osteosynthesis failure was 12.2% (5 of 41). Two failures were observed in 21 patients with open reductions and plate fixations, compared with three failures in 20 procedures involving closed reductions and intramedullary stabilization. The 1- and 2-year survival rates were 0.35 and 0.2 in ORIF and 0.07 and 0 in patients with IM fixation retrospectively. CONCLUSION: Intramedullary stabilization is a reliable method for fixation of pathologic fractures of the humerus diaphysis for patients in the advanced stage of metastatic disease. ORIF are preferable to IM fixations for the treatment of metaphyseal fractures and for those patients with a solitary metastasis in the humerus or those with a better prognosis.

Mason type-I radial head fractures and interosseous membrane lesions--a prospective study.

BACKGROUND: The role of the forearm interosseous membrane (IOM) in trauma remains not fully understood. Information from experimental models simulating sudden axial loading of the IOM is limited. The results from several cadaver studies are controversially discussed in literature. Pronation and supination of the forearm as well as varus and valgus position of the elbow joint have been suspected to have influence on the injury pattern. The purpose of the current study, therefore, was to further investigate the role of the IOM in trauma mechanism. METHODS: We prospectively screened the forearms of 14 patients with Mason type-I radial head fractures for additional occult IOM lesions. The fractures were classified according to the Mason classification using plain radiographs. All patients were subjected to forearm magnetic resonance imaging visualizing the entire IOM within a week. Treatment consisted of nearly total immobilization of the elbow joint using a special elastic and gauze bandage for 7 days followed by an early motion recovery program. RESULTS: Partial disruptions of the distal part of the IOM were found in nine cases. The biomechanically essential interosseous ligament was not attained by these ruptures in any of the cases. None of the patient had the classical findings of the Essex Lopresti lesion. All patients had regular roentgenograms of both wrists. Patients were asymptomatic at the time of a 4-week follow-up. CONCLUSION: Our results suggest that injuries of the IOM are more frequent than generally expected. The findings support the conclusions of some of the previous cadaver studies. If IOM lesions are suspected, magnetic resonance imaging tomography should be performed.

Biomechanical comparison of modified Kessler and running suture repair in 3 different animal tendons and in human flexor tendons.

PURPOSE: To establish the animal flexor tendon that best mimics the biomechanical performance of human flexor tendons. We investigated the biomechanical behavior of core and running sutures in 3 different animal flexor tendons and in human flexor tendons. Additionally, we attempted to help standardize future flexor tendon studies. To that purpose, nearly all variables occurring in the test setup have been highlighted. METHODS: The species selected were pig, calf, sheep, and human. Two groups were formed. In the first group we tested 3-0 core sutures (Ticron; Tyco Healthcare, Vienna, Austria), and in the second group we tested 5-0 running sutures (Ethilon; Ethicon, Vienna, Austria). In each group, 10 tendons of each specimen were tested, which yielded a total of 80 tendons. In each group, the repaired tendons were subjected to 3,000 linear load cycles at a load of 15 N. At the end of this procedure, final gap values were recorded. In the next step, ultimate load-to-failure data were obtained from each specimen. RESULTS: Core sutures behaved similarly in the human, sheep, and pig tendons with respect to ultimate loads. With respect to gap formation, core sutures behaved similarly in the human, sheep, and calf tendons. Deep running sutures behaved similarly in the human, sheep, and pig tendons in terms of ultimate load to failure. CONCLUSIONS: In this study, sheep tendons were found to best mimic the biomechanical behavior of human tendons. Calf tendons seem to be unsuitable. There is a strong need for consistency in biomechanical test setups.