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The functionalization of metal-organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalized with chloro groups. Notably, MFM-68-Cl 2 , constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g -1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy, and inelastic neutron scattering, coupled with density functional theory modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl 2 . This study represents the first example of enhanced adsorption of trace benzene promoted by -C H ···Cl and Cl···π interactions in porous materials.

3D electron diffraction (3DED) is increasingly employed to determine molecular and crystal structures from micro-crystals. Indomethacin is a well known, marketed, small-molecule non-steroidal anti-inflammatory drug with eight known polymorphic forms, of which four structures have been elucidated to date. Using 3DED, we determined the structure of a new ninth polymorph, σ, found within an amorphous solid dispersion, a product formulation sometimes used for active pharmaceutical ingredients with poor aqueous solubility. Subsequently, we found that σ indomethacin can be produced from direct solvent evaporation using dichloromethane. These results demonstrate the relevance of 3DED within drug development to directly probe product formulations., (open access.)

The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare MOF materials bearing free, accessible -COOH moieties which would normally bind to metal ions within the framework structure. Here, we describe the direct binding of CO 2 and C 2 H 2 molecules to the free -COOH sites within the pores of MFM-303(Al). MFM-303(Al) exhibits highly selective adsorption of CO 2 and C 2 H 2 with a high selectivity for C 2 H 2 over C 2 H 4 . In situ synchrotron X-ray diffraction and inelastic neutron scattering, coupled with modelling, highlight the cooperative interactions of adsorbed CO 2 and C 2 H 2 molecules with free -COOH and -OH sites within MFM-303(Al), thus rationalising the observed high selectivity for gas separation., Competing Interests: The authors declare no competing interest., (This journal is © The Royal Society of Chemistry.)

Formamides are important feedstocks for the manufacture of many fine chemicals. State-of-the-art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom-economy. Here, we report the first example of direct synthesis of N-formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass-derived aldehydes and ketones, and fixation of CO 2 in the presence of H 2 over a metal-organic framework supported ruthenium catalyst, Ru/MFM-300(Cr). Highly selective production of N-formamides has been observed for a wide range of carbonyl compounds. Synchrotron X-ray powder diffraction reveals the presence of strong host-guest binding interactions via hydrogen bonding and parallel-displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO 2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Deuterium labelling of organic compounds is an important process in chemistry. We report the first example of photocatalytic dehalogenative deuteration of both arylhalides and alkylhalides (40 substrates) over a metal-organic framework, MFM-300(Cr), using CD 3 CN as the deuterium source at room temperature. MFM-300(Cr) catalyses high deuterium incorporation and shows excellent tolerance to various functional groups. Synchrotron X-ray powder diffraction reveals the activation of halogenated substrates via confined binding within MFM-300(Cr). In situ electron paramagnetic resonance spectroscopy confirms the formation of carbon-based radicals as intermediates and reveals the reaction pathway. This protocol removes the use of precious-metal catalysts from state-of-the-art processes based upon direct hydrogen isotope exchange and shows high photocatalytic stability, thus enabling multiple catalytic cycles., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The structure and vibrational spectroscopy of centrohexaindane, 1, was investigated. This unusual molecule has a quaternary carbon atom that is coordinated to four further such quaternary carbon atoms as its core, each pair of which is bonded to an ortho-phenylene unit. Previous NMR studies have shown that the molecule has tetrahedral (T d ) symmetry in solution. The infrared and Raman spectra of chloroform and deuterochloroform solutions of 1 are completely in agreement with this conclusion, as the only modes that are visible are those allowed for T d symmetry. This is not the case in the solid state: X-ray powder diffraction indicates that the unit cell is triclinic or monoclinic with a volume in excess of 4000 Å 3 . The vibrational spectroscopy is consistent with C 1 site symmetry and the presence of at least two molecules in the primitive cell. It is likely that the space group is centrosymmetric., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The interactions between adsorbed gas molecules within porous metal-organic frameworks are crucial to gas selectivity but remain poorly explored. Here, we report the modulation of packing geometries of CO 2 and C 2 H 2 clusters within the ultramicroporous CUK-1 material as a function of temperature. In-situ synchrotron X-ray diffraction reveals a unique temperature-dependent reversal of CO 2 and C 2 H 2 adsorption affinities on CUK-1, which is validated by gas sorption and dynamic breakthrough experiments, affording high-purity C 2 H 2 (99.95%) from the equimolar mixture of C 2 H 2 /CO 2 via a one-step purification process. At low temperatures (<253 K), CUK-1 preferentially adsorbs CO 2 with both high selectivity (>10) and capacity (170 cm 3 g -1 ) owing to the formation of CO 2 tetramers that simultaneously maximize the guest-guest and host-guest interactions. At room temperature, conventionally selective adsorption of C 2 H 2 is observed. The selectivity reversal, structural robustness, and facile regeneration of CUK-1 suggest its potential for producing high-purity C 2 H 2 by temperature-swing sorption., (© 2023. The Author(s).)

A cross-coupling reaction via the dehydrogenative route over heterogeneous solid atomic catalysts offers practical solutions toward an economical and sustainable elaboration of simple organic substrates. The current utilization of this technology is, however, hampered by limited molecular definition of many solid catalysts. Here, we report the development of Cu-M dual-atom catalysts (where M = Co, Ni, Cu, and Zn) supported on a hierarchical USY zeolite to mediate efficient dehydrogenative cross-coupling of unprotected phenols with amine partners. Over 80% isolated yields have been attained over Cu-Co-USY, which shows much superior reactivity when compared with our Cu 1 and other Cu-M analogues. This amination reaction has hence involved simple and non-forceful reaction condition requirements. The superior reactivity can be attributed to (1) the specifically designed bimetallic Cu-Co active sites within the micropore for "co-adsorption-co-activation" of the reaction substrates and (2) the facile intracrystalline (meso/micropore) diffusion of the heterocyclic organic substrates. This study offers critical insights into the engineering of next-generation solid atomic catalysts with complex reaction steps.

Increasing levels of air pollution are driving the need for the development of new processes that take "waste-to-chemicals". Herein, we report the capture and conversion under ambient conditions of a major air pollutant, NO 2 , using a robust metal-organic framework (MOF) material, Zr-bptc (H 4 bptc = 3,3',5,5'-biphenyltetracarboxylic acid), comprising {Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (COO) 12 } clusters linked by 4-connected bptc 4- ligands in an ftw topology. At 298 K, Zr-bptc shows exceptional stability and adsorption of NO 2 at both low (4.9 mmol g -1 at 10 mbar) and high pressures (13.8 mmol g -1 at 1.0 bar), as measured by isotherm experiments. Dynamic breakthrough experiments have confirmed the selective retention of NO 2 by Zr-bptc at low concentrations under both dry and wet conditions. The immobilized NO 2 can be readily transformed into valuable nitro compounds relevant to construction, agrochemical, and pharmaceutical industries. In situ crystallographic and spectroscopic studies reveal strong binding interactions of NO 2 to the {Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (COO) 12 } cluster node. This study paves a circular pathway to enable the integration of nitrogen-based air pollutants into the production of fine chemicals.

The development of cost-effective sorbents for direct capture of trace CO 2 (<1 %) from the atmosphere is an important and challenging task. Natural or commercial zeolites are promising sorbents, but their performance in adsorption of trace CO 2 has been poorly explored to date. A systematic study on capture of trace CO 2 by commercial faujasite zeolites reveals that the extra-framework cations play a key role on their performance. Under dry conditions, Ba-X displays high dynamic uptake of 1.79 and 0.69 mmol g -1 at CO 2 concentrations of 10000 and 1000 ppm, respectively, and shows excellent recyclability in the temperature-swing adsorption processes. K-X exhibits perfect moisture resistance, and >95 % dry CO 2 uptake can be preserved under relative humidity of 74 %. In situ solid-state NMR spectroscopy, synchrotron X-ray diffraction and neutron diffraction reveal two binding sites for CO 2 in these zeolites, namely the basic framework oxygen atoms and the divalent alkaline earth metal ions. This study unlocks the potential of low-cost natural zeolites for applications in direct air capture., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We report reversible high capacity adsorption of SO 2 in robust Zr-based metal-organic framework (MOF) materials. Zr-bptc (H 4 bptc=biphenyl-3,3',5,5'-tetracarboxylic acid) shows a high SO 2 uptake of 6.2 mmol g -1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO 2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed Cu II or heteroatomic sulphur sites into the pores enhance the capture of SO 2 at low concentrations. The captured SO 2 can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO 2 molecules and host-guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The development of materials showing rapid proton conduction with a low activation energy and stable performance over a wide temperature range is an important and challenging line of research. Here, we report confinement of sulfuric acid within porous MFM-300(Cr) to give MFM-300(Cr)·SO 4 (H 3 O) 2 , which exhibits a record-low activation energy of 0.04 eV, resulting in stable proton conductivity between 25 and 80 °C of >10 -2 S cm -1 . In situ synchrotron X-ray powder diffraction (SXPD), neutron powder diffraction (NPD), quasielastic neutron scattering (QENS), and molecular dynamics (MD) simulation reveal the pathways of proton transport and the molecular mechanism of proton diffusion within the pores. Confined sulfuric acid species together with adsorbed water molecules play a critical role in promoting the proton transfer through this robust network to afford a material in which proton conductivity is almost temperature-independent.

The precipitation of hydrated phases from a chondrite-like Na-Mg-Ca-SO 4 -Cl solution is studied using in situ synchrotron X-ray powder diffraction, under rapid- (360 K h -1 , T = 250-80 K, t = 3 h) and ultra-slow-freezing (0.3 K day -1 , T  = 273-245 K, t = 242 days) conditions. The precipitation sequence under slow cooling initially follows the predictions of equilibrium thermodynamics models. However, after ∼50 days at 245 K, the formation of the highly hydrated sulfate phase Na 2 Mg(SO 4 ) 2 ·16H 2 O, a relatively recent discovery in the Na 2 Mg(SO 4 ) 2 -H 2 O system, was observed. Rapid freezing, on the other hand, produced an assemblage of multiple phases which formed within a very short timescale (≤4 min, Δ T = 2 K) and, although remaining present throughout, varied in their relative proportions with decreasing temperature. Mirabilite and meridianiite were the major phases, with pentahydrite, epsomite, hydrohalite, gypsum, blödite, konyaite and loweite also observed. Na 2 Mg(SO 4 ) 2 ·16H 2 O was again found to be present and increased in proportion relative to other phases as the temperature decreased. The results are discussed in relation to possible implications for life on Europa and application to other icy ocean worlds., (© Stephen P. Thompson et al. 2021.)

Neutral ketene is a crucial intermediate during zeolite carbonylation reactions. In this work, the roles of ketene and its derivates (viz., acylium ion and surface acetyl) associated with direct C-C bond coupling during the carbonylation reaction have been theoretically investigated under realistic reaction conditions and further validated by synchrotron radiation X-ray diffraction (SR-XRD) and Fourier transformed infrared (FT-IR) studies. It has been demonstrated that the zeolite confinement effect has significant influence on the formation, stability, and further transformation of ketene. Thus, the evolution and the role of reactive and inhibitive intermediates depend strongly on the framework structure and pore architecture of the zeolite catalysts. Inside side pockets of mordenite (MOR), rapid protonation of ketene occurs to form a metastable acylium ion exclusively, which is favorable toward methyl acetate (MA) and acetic acid (AcOH) formation. By contrast, in 12MR channels of MOR, a relatively longer lifetime was observed for ketene, which tends to accelerate deactivation of zeolite due to coke formation by the dimerization of ketene and further dissociation to diene and alkyne. Thus, we resolve, for the first time, a long-standing debate regarding the genuine role of ketene in zeolite catalysis. It is a paradigm to demonstrate the confinement effect on the formation, fate, and catalytic consequence of the active intermediates in zeolite catalysis.

Selective oxidation of benzylic C-H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metal catalysts. Herein, we report the efficient oxidation of benzylic C-H groups in a broad range of substrates under mild conditions over a robust metal-organic framework material, MFM-170, incorporating redox-active [Cu 2 II (O 2 CR) 4 ] paddlewheel nodes. A comprehensive investigation employing electron paramagnetic resonance (EPR) spectroscopy and synchrotron X-ray diffraction has identified the critical role of the paddlewheel moiety in activating the oxidant t BuOOH (tert-butyl hydroperoxide) via partial reduction to [Cu II Cu I (O 2 CR) 4 ] species., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We present the robotic harvest of a pedicled omentum flap for reconstruction of a near-total anterior chest wall defect. The patient was a 68-year-old woman with recurrent secondary chest wall angiosarcoma after previous mastectomy and radiation therapy. She underwent neoadjuvant chemotherapy and radiation, followed by wide radical chest wall resection with a final defect size of 15×35 cm. A one-stage reconstruction was performed with an omentum flap harvested by robotic technique and split-thickness skin grafts from thigh donor sites. The patient healed with minimal complications. Our case supports more widespread application of robotics in plastic and reconstructive surgery., Competing Interests: Competing interests: None declared., (© BMJ Publishing Group Limited 2021. No commercial re-use. See rights and permissions. Published by BMJ.)

Ni-rich layered cathode materials are among the most promising candidates for high-energy-density Li-ion batteries, yet their degradation mechanisms are still poorly understood. We report a structure-driven degradation mechanism for NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ), in which a proportion of the material exhibits a lowered accessible state of charge at the end of charging after repetitive cycling and becomes fatigued. Operando synchrotron long-duration X-ray diffraction enabled by a laser-thinned coin cell shows the emergence and growth in the concentration of this fatigued phase with cycle number. This degradation is structure driven and is not solely due to kinetic limitations or intergranular cracking: no bulk phase transformations, no increase in Li/Ni antisite mixing and no notable changes in the local structure or Li-ion mobility of the bulk are seen in aged NMCs. Instead, we propose that this degradation stems from the high interfacial lattice strain between the reconstructed surface and the bulk layered structure that develops when the latter is at states of charge above a distinct threshold of approximately 75%. This mechanism is expected to be universal in Ni-rich layered cathodes. Our findings provide fundamental insights into strategies to help mitigate this degradation process.

Temperature- or pressure-swing sorption in porous metal-organic framework (MOF) materials has been proposed for new gas separation technologies. The high tunability of MOFs toward particular adsorbates and the relatively low energy penalty for system regeneration indicate that reversible physisorption in MOFs has the potential to create economic and environmental benefits compared with state-of-the-art chemisorption systems. However, for MOF-based sorbents to be commercialized, they have to show long-term stability under the conditions imposed by the application. Here, we demonstrate the structural stability of MFM-300(Al) in the presence of a series of industrially relevant toxic and corrosive gases, including SO 2 , NO 2 , and NH 3 , over 4 years using long-duration synchrotron X-ray powder diffraction. Full structural analysis of gas-loaded MFM-300(Al) confirms the retention of these toxic gas molecules within the porous framework for up to 200 weeks, and cycling adsorption experiments verified the reusability of MFM-300(Al) for the capture of these toxic air pollutants.

This article highlights the recent fundamental study in using achiral and chiral porous materials for the potential applications in asymmetric catalysis. Thanks to the new-generation synchrotron X-ray powder diffraction (SXRD) facilities, we reveal the presence of the unique 'chiral region' in achiral zeolites with the MFI topology. Both the inherent site-isolation effect of the active sites and internal confinement restraints in zeolites are critical for creating 'chiral regions' that can aid the design of more enantioselective catalytic reactions. We also offer an outlook on the challenges and opportunities of this research area.

The clean and reproducible conditions provided by microfluidic devices are ideal sample environments for in situ analyses of chemical and biochemical reactions and assembly processes. However, the small size of microchannels makes investigating the crystallization of poorly soluble materials on-chip challenging due to crystal nucleation and growth that result in channel fouling and blockage. Here, we demonstrate a reusable insert-based microfluidic platform for serial X-ray diffraction analysis and examine scale formation in response to continuous and segmented flow configurations across a range of temperatures. Under continuous flow, scale formation on the reactor walls begins almost immediately on mixing of the crystallizing species, which over time results in occlusion of the channel. Depletion of ions at the start of the channel results in reduced crystallization towards the end of the channel. Conversely, segmented flow can control crystallization, so it occurs entirely within the droplet. Consequently, the spatial location within the channel represents a temporal point in the crystallization process. Whilst each method can provide useful crystallographic information, time-resolved information is lost when reactor fouling occurs and changes the solution conditions with time. The flow within a single device can be manipulated to give a broad range of information addressing surface interaction or solution crystallization.

Understanding the transitions between polymorphs is essential in the development of strategies for manufacturing and maximizing the efficiency of pharmaceuticals. However, this can be extremely challenging: crystallization can be influenced by subtle changes in environment, such as temperature and mixing intensity or even imperfections in the crystallizer walls. Here, we highlight the importance of in situ measurements in understanding crystallization mechanisms, where a segmented flow crystallizer was used to study the crystallization of the pharmaceuticals urea: barbituric acid (UBA) and carbamazepine (CBZ). The reactor provides highly reproducible reaction conditions, while in situ synchrotron powder X-ray diffraction (PXRD) enables us to monitor the evolution of this system. UBA has two polymorphs of almost equivalent free-energy and so is typically obtained as a polymorphic mixture. In situ PXRD analysis uncovered a progression of polymorphs from UBA III to the thermodynamic polymorph UBA I, where different positions along the length of the tubular flow crystallizer correspond to different reaction times. Addition of UBA I seed crystals modified this pathway such that only UBA I was observed throughout, while transformation from UBA III into UBA I still occurred in the presence of UBA III seeds. Information regarding the mixing-dependent kinetics of the CBZ form II to III transformation was also uncovered in a series of seeded and unseeded flow crystallization runs, despite atypical habit expression. These results illustrate the importance of coupling controlled reaction environments with in situ XRD to study the phase relationships in polymorphic materials.

Background: There is sparse literature studying the functional morbidity of subpectoral implant- based breast reconstruction. We aimed to prospectively investigate this technique's impact on objective upper extremity function and patient-reported outcomes., Methods: Women undergoing mastectomy and immediate subpectoral tissue expander insertion with ADM sling were enrolled from November 2014 to August 2016. Preoperative evaluation of shoulder range of motion, pectoralis major strength, and Quick Disabilities of the Arm, Shoulder, and Hand (QuickDASH) and Breast-Q surveys were conducted before surgery and at 1 month and 6 months postoperatively, or until return to baseline pectoralis major strength., Results: Eighteen women (mean age, 51 years, SD 9.6, range 35-72 years) comprising 26 breast reconstructions completed postoperative follow-up. The average follow-up length was 9 months (range, 3 -18 months; SD, 144 days). At 1-month follow-up, there was a statistically significant decrease in lower and non dominant upper fiber pectoralis strength from preoperative baseline (p < 0.05). At final postoperative follow-up, 24 reconstructions (92.3%) recovered to at least 80% of preoperative strength in upper and lower fibers. From preoperative to final postoperative follow-up, QuickDASH scores showed a statistically significant (p = 0.008) increase from 4.1 (range 0-20.5, SD 6.1) to 18.7 (range 0-45.5, SD 13.4). Physical well-being: The chest was the only Breast-Q domain in which the average score significantly decreased (p = 0.02) between preoperative assessment and final follow-up., Conclusions: After implant-based breast reconstruction, patients achieve the return of objective upper extremity function, but patient-reported outcomes do not return to baseline as shown by increased QuickDASH scores. Thus, pectoralis-sparing reconstructive strategies such as prepectoral implant insertion should be pursued., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Emissions of SO 2 from flue gas and marine transport have detrimental impacts on the environment and human health, but SO 2 is also an important industrial feedstock if it can be recovered, stored and transported efficiently. Here we report the exceptional adsorption and separation of SO 2 in a porous material, [Cu 2 (L)] (H 4 L = 4',4‴-(pyridine-3,5-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid)), MFM-170. MFM-170 exhibits fully reversible SO 2 uptake of 17.5 mmol g -1 at 298 K and 1.0 bar, and the SO 2 binding domains for trapped molecules within MFM-170 have been determined. We report the reversible coordination of SO 2 to open Cu(II) sites, which contributes to excellent adsorption thermodynamics and selectivities for SO 2 binding and facile regeneration of MFM-170 after desorption. MFM-170 is stable to water, acid and base and shows great promise for the dynamic separation of SO 2 from simulated flue gas mixtures, as confirmed by breakthrough experiments.

We report the precise postsynthetic control of the composition of β-Fe 1+x Se by electrochemistry with simultaneous tracking of the associated structural changes via in situ synchrotron X-ray diffraction. We access the full phase width of 0.011+x Se forms a new phase in the presence of oxygen above a 100 °C which has the same anti-PbO type structure but is not superconducting down to 1.8 K. The latter process can be reversed electrochemically to reinstate the superconducting state. These observations exploit the exquisite control afforded by electrochemistry in contrast with classical approaches of chemical synthesis., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Abdominoperineal resection is the treatment for many anorectal malignancies. The laparotomy approach allows for harvest of the rectus abdominis muscle for perineal reconstruction. However, with increasing numbers of robotic abdominoperineal resections being performed, the morbidity associated with a laparotomy incision is avoided. We describe a modification of the previous technique of advancing bilateral fasciocutaneous gluteal flaps into the pelvic cavity for reconstruction. This operation is performed expeditiously in the prone position. The patient is spared a large anterior deficit but reaps the benefits of a robust reconstruction with minimal morbidity., Methods: A retrospective chart review was performed from July 2012 to February 2018 of our institution's electronic record database. All patients who underwent modified V-Y gluteal fasciocutaneous flaps for perineal defects were included. Patient demographics, comorbidities, and adjunctive therapies as well as outcomes and complications were analyzed., Results: A total of 31 patients (51 flaps) were identified with 100% flap survival. The total number of patients with minor complications was 42%, consisting of 4 surgical site infections (13%), 13 cases of dehiscence (42%), and 2 cases requiring return to the operating room for abscess drainage (6%). Importantly, dehiscence was defined as any wound separation, regardless of size, with an average of only 3.8 cm. All healed with conservative management. After foregoing bolstering with synthetic mesh, the complication rate decreased from 67% to 37% (odds ratio, 3.4; P = 0.11)., Conclusions: This modified technique of bilateral fasciocutaneous gluteal V-Y advancement flaps for perineal wound control is a safe and effective method of reconstructing defects.

Liquid oceans and ice caps, along with ice crusts, have long been considered defining features of the Earth, but space missions and observations have shown that they are in fact common features among many of the solar system's outer planets and their satellites. Interactions with rock-forming materials have produced saline oceans not dissimilar in many respects to those on Earth, where mineral precipitation within frozen seawater plays a significant role in both determining global properties and regulating the environment in which a complex ecosystem of extremophiles exists. Since water is considered an essential ingredient for life, the presence of oceans and ice on other solar system bodies is of great astrobiological interest. However, the details surrounding mineral precipitation in freezing environments are still poorly constrained, owing to the difficulties of sampling and ex situ preservation for laboratory analysis, meaning that predictive models have limited empirical underpinnings. To address this, the design and performance characterization of a transmission-geometry sample cell for use in long-duration synchrotron X-ray powder diffraction studies of in situ mineral precipitation from aqueous ice-brine systems are presented. The cell is capable of very slow cooling rates ( e.g. 0.3°C per day or less), and its performance is demonstrated with the results from a year-long study of the precipitation of the hydrated magnesium sulfate phase meridianiite (MgSO 4 ·11H 2 O) from the MgSO 4 -H 2 O system. Evidence from the Mars Rover mission suggests that this hydrated phase is widespread on the present-day surface of Mars. However, as well as the predicted hexagonal ice and meridianiite phases, an additional hydrated sulfate phase and a disordered phase are observed.

Background: The evolution of three-dimensional printing into prosthetics has opened conversations about the availability and cost of prostheses. This report will discuss how a prosthetic team incorporated additive manufacture techniques into the treatment of a patient with a partial hand amputation to create and test a unique assistive device which he could use to hold his French horn. Case description and methods: Using a process of shape capture, photogrammetry, computer-aided design and finite element analysis, a suitable assistive device was designed and tested. The design was fabricated using three-dimensional printing. Patient satisfaction was measured using a Pugh's Matrix™, and a cost comparison was made between the process used and traditional manufacturing. Findings and outcomes: Patient satisfaction was high. The three-dimensional printed devices were 56% cheaper to fabricate than a similar laminated device., Conclusion: Computer-aided design and three-dimensional printing proved to be an effective method for designing, testing and fabricating a unique assistive device. Clinical relevance CAD and 3D printing techniques can enable devices to be designed, tested and fabricated cheaper than when using traditional techniques. This may lead to improvements in quality and accessibility.

A software package for the calibration and processing of powder X-ray diffraction and small-angle X-ray scattering data is presented. It provides a multitude of data processing and visualization tools as well as a command-line scripting interface for on-the-fly processing and the incorporation of complex data treatment tasks. Customizable processing chains permit the execution of many data processing steps to convert a single image or a batch of raw two-dimensional data into meaningful data and one-dimensional diffractograms. The processed data files contain the full data provenance of each process applied to the data. The calibration routines can run automatically even for high energies and also for large detector tilt angles. Some of the functionalities are highlighted by specific use cases.

A new synchrotron X-ray powder diffraction instrument has been built and commissioned for long-duration experiments on beamline I11 at Diamond Light Source. The concept is unique, with design features to house multiple experiments running in parallel, in particular with specific stages for sample environments to study slow kinetic systems or processes. The instrument benefits from a high-brightness X-ray beam and a large area detector. Diffraction data from the commissioning work have shown that the objectives and criteria are met. Supported by two case studies, the results from months of measurements have demonstrated the viability of this large-scale instrument, which is the world's first dedicated facility for long-term studies (weeks to years) using synchrotron radiation.

The polar corundum structure type offers a route to new room temperature multiferroic materials, as the partial LiNbO 3 -type cation ordering that breaks inversion symmetry may be combined with long-range magnetic ordering of high spin d 5 cations above room temperature in the AFeO 3 system. We report the synthesis of a polar corundum GaFeO 3 by a high-pressure, high-temperature route and demonstrate that its polarity arises from partial LiNbO 3 -type cation ordering by complementary use of neutron, X-ray, and electron diffraction methods. In situ neutron diffraction shows that the polar corundum forms directly from AlFeO 3 -type GaFeO 3 under the synthesis conditions. The A 3+ /Fe 3+ cations are shown to be more ordered in polar corundum GaFeO 3 than in isostructural ScFeO 3 . This is explained by DFT calculations which indicate that the extent of ordering is dependent on the configurational entropy available to each system at the very different synthesis temperatures required to form their corundum structures. Polar corundum GaFeO 3 exhibits weak ferromagnetism at room temperature that arises from its Fe 2 O 3 -like magnetic ordering, which persists to a temperature of 408 K. We demonstrate that the polarity and magnetization are coupled in this system with a measured linear magnetoelectric coupling coefficient of 0.057 ps/m. Such coupling is a prerequisite for potential applications of polar corundum materials in multiferroic/magnetoelectric devices.

In operando synchrotron X-ray powder diffraction (SXPD) studies were conducted to investigate the phase transition of Li-rich Li(Li0.2Ni0.13Mn0.54Co0.13)O2 and Cr-doped Li(Li0.2Ni0.13Mn0.54Co0.03Cr0.10)O2 cathodes during the first charge/discharge cycle. Crystallographic (lattice parameters) and mechanical (domain size and microstrain) information was collected from SXPD full pattern refinement. It was found that Cr substitution at Co-site benefits in suppressing the activation of Li2MnO3 domains upon 1st charge, and thus mitigates the phase transition. As a consequence, Cr-doped layered cathode holds a better reversibility in terms of a full recovery of both lattice parameters and nano-domain size after a whole charge/discharge cycle. The effects of different cycling rates on the structural change were also discussed.

Selenium (Se) reservoirs in coal waste rock from the Elk Valley, southeastern British Columbia, the location of Canada's major steelmaking coal mines, were characterized and quantified by analyzing samples collected from the parent rock, freshly blasted waste rock (less than 10 days old), and aged waste rock (deposited between 1982 and 2012). Se is present throughout the waste rock dumps at a mean digestible (SeD) concentration of 3.12 mg/kg. Microprobe analyses show that Se is associated with the primary minerals sphalerite, pyrite, barite, and chalcopyrite and secondary Fe oxyhydroxides. Selenium K-edge X-ray absorption near-edge spectroscopy analyses indicate that, on average, 21% of Se is present as selenide (Se(2-)) in pyrite and sphalerite, 19% of Se is present as selenite (Se(4+)) in barite, 21% of Se is present as exchangeable Fe oxyhydroxide and clay-adsorbed Se(4+), and 39% of Se is present as organoselenium associated with coaly matter. The dominant source minerals for aqueous-phase Se are pyrite and sphalerite. Secondary Fe oxyhydroxide sequesters, on average, 37% of Se released by pyrite oxidation. Measured long-term Se fluxes from a rock drain at the base of a waste dump suggest that at least 20% of Se(2-)-bearing sulfides were oxidized and released from that dump over the past 30 year period; however, the Se mass lost was not evident in SeD analyses.

Student perspectives reflect school climate. The study examined perspectives among deaf and hard of hearing students in residential and large day schools regarding bullying, and compared these perspectives with those of a national database of hearing students. The participants were 812 deaf and hard of hearing students in 11 U.S. schools. Data were derived from the Olweus Bullying Questionnaire (Olweus, 2007b), a standardized self-reported survey with multiple-choice questions focusing on different aspects of bullying problems. Significant bullying problems were found in deaf school programs. It appears that deaf and hard of hearing students experience bullying at rates 2-3 times higher than those reported by hearing students. Deaf and hard of hearing students reported that school personnel intervened less often when bullying occurred than was reported in the hearing sample. Results indicate the need for school climate improvement for all students, regardless of hearing status.

Spontaneous combustion and low-temperature oxidation of waste coal and other carbonaceous material at open-cut coal mines are potentially significant sources of greenhouse gas emissions. However, the magnitude of these emissions is largely unknown. In this study, emissions from spontaneous combustion and low-temperature oxidation were estimated for six Australian open-cut coal mines with annual coal production ranging from 1.7 to more than 16 Mt. Greenhouse emissions from all other sources at these mines were also estimated and compared to those from spontaneous combustion and low-temperature oxidation. In all cases, fugitive emission of methane was the largest source of greenhouse gas; however, in some mines, spontaneous combustion accounted for almost a third of all emissions. For one mine, it was estimated that emissions from spontaneous combustion were around 250,000 t CO(2)-e per annum. The contribution from low-temperature oxidation was generally less than about 1% of the total for all six mines. Estimating areas of spoil affected by spontaneous combustion by ground-based surveys was prone to under-report the area. Airborne infrared imaging appears to be a more reliable method.