Cyclopropenimine-Mediated CO2 Activation for the Synthesis of Polyurethanes and Small-Molecule Carbonates and Carbamates.

Carbon dioxide (CO2) is an abundant C1 feedstock with tremendous potential to produce versatile building blocks in synthetic applications. Given the adverse impact of CO2 on the atmosphere, it is of paramount importance to devise strategies for upcycling it into useful materials, such as polymers and fine chemicals. To activate such stable molecule, superbases offer viable modes of binding to CO2. In this study, a superbase cyclopropenimine derivative was found to exhibit exceptional proficiency in activating CO2 and mediating its polymerization at ambient temperature and pressure for the synthesis of polyurethanes. The versatility of this reaction can be extended to monofunctional amines and alcohols, yielding a variety of functional carbonates and carbamates.

Probing magnetic properties at the nanoscale: in-situ Hall measurements in a TEM.

We report on advanced in-situ magneto-transport measurements in a transmission electron microscope. The approach allows for concurrent magnetic imaging and high resolution structural and chemical characterization of the same sample. Proof-of-principle in-situ Hall measurements on presumably undemanding nickel thin films supported by micromagnetic simulations reveal that in samples with non-trivial structures and/or compositions, detailed knowledge of the latter is indispensable for a thorough understanding and reliable interpretation of the magneto-transport data. The proposed in-situ approach is thus expected to contribute to a better understanding of the Hall signatures in more complex magnetic textures.

Effect of Solvent on the Rate of Ozonolysis: Development of a Homogeneous Flow Ozonolysis Protocol.

Herein, we describe the effect of organic solvents on ozone solubility and the rate of ozonolysis reactions using rapid injection NMR spectroscopy. The tabulated solubility and kinetic data allowed for the design of a homogeneous ozonolysis flow reactor capable of delivering precise quantities of dissolved ozone to various olefin substrates.

Capturing primary ozonides for a syn-dihydroxylation of olefins.

Ozonolysis is a widely used and practical synthetic technique for the deconstructive oxidation of olefins using ozone. While there are numerous ozonolysis reactions that give a myriad of products and functionalities, almost all of them involve scission at the olefin double bond. Using ozone as a constructive reagent rather than a deconstructive one would open new domains of chemical reactivity and amplify molecular complexity in synthetic methodology. Here we report the use of primary ozonides as preparative synthetic intermediates for a safe and green olefin syn-dihydroxylation reaction. Furthermore, we have demonstrated this method using a continuous flow reactor that virtually eliminates peroxide accumulation and extended these applications towards the synthesis of pharmaceutically relevant small molecules such as guaifenesin, the active ingredient in Mucinex, and a precursor to ponesimod, a drug to treat multiple sclerosis.

Breaking the tert-Butyllithium Contact Ion Pair: A Gateway to Alternate Selectivity in Lithiation Reactions.

The effects of Lewis basic phosphoramides on the aggregate structure of t-BuLi have been investigated in detail by NMR and DFT methods. It was determined that hexamethylphosphoramide (HMPA) can shift the equilibrium of t-BuLi to include the triple ion pair (t-Bu-Li-t-Bu)-/HMPA4Li+ which serves as a reservoir for the highly reactive separated ion pair t-Bu-/HMPA4Li+. Because the Li-atom's valences are saturated in this ion pair, the Lewis acidity is significantly decreased; in turn, the basicity is maximized which allowed for the typical directing effects within oxygen heterocycles to be overridden and for remote sp3 C-H bonds to be deprotonated. Furthermore, these newly accessed lithium aggregation states were leveraged to develop a simple γ-lithiation and capture protocol of chromane heterocycles with a variety of alkyl halide electrophiles in good yields.

Preparation of Highly Reactive Lithium Metal Dendrites for the Synthesis of Organolithium Reagents.

A long-standing problem in the area of organolithium chemistry has been the need for a highly reactive Li-metal source that mimics Li-powders but has the advantage of being freshly prepared from inexpensive and readily available Li-sources. Here, we report a simple and convenient activation method using liquid ammonia that furnishes a new Li-metal source in the form of crystalline Li-dendrites. The Li-dendrites were shown to have ca. 100 times greater surface area than conventional Li-sources created by prototypical mechanical activation methods. Concomitant with the surface area increase, the Li-dendrites were shown to exhibit significant rate enhancements over Li-powders, which are currently the industry standard for the preparation of organolithium compounds. These features were leveraged for the reproducible synthesis of organolithium reagents over a range of common laboratory scales.

The impact on emotional well-being of being a palliative care volunteer: An interpretative phenomenological analysis.

BACKGROUND: Much palliative care provision relies on the support of volunteers. Attention is paid to the risks to professionals providing care, such as stress and burnout, but understanding if this is an issue for volunteers is little understood. It is important to understand the impact their role has on volunteers emotional well-being. AIM: To explore the experiences of palliative care volunteers and how the role impacted on their emotional well-being. DESIGN: Interpretative phenomenological analysis, with data collected through semi-structured interviews. SETTING/PARTICIPANTS: Volunteers in patient-facing roles within palliative and end-of-life care services in the UK. RESULTS: Volunteers (n = 10) across three palliative and end-of-life care services. Four themes were developed: (1) it can be challenging; (2) it's where I'm meant to be; (3) managing death; (4) the importance of connection. Challenges included frustrations and questioning themselves. Although difficult at times, volunteers expressed the importance of the role, doing well and that they benefitted too. They also had to manage death and discussed beliefs about life and death, acceptance and managing patients' fears. Connection with the hospice, patients, staff and other volunteers was important, with a need for everyone to feel valued. CONCLUSIONS: Although there are psychosocial benefits for volunteers in their role, it is important to understand the challenges faced and consider ongoing support to help volunteers manage these challenges. This could be addressed through the consideration of coping mechanisms, further training and reflective practice for volunteers.

Signatures of the Magnetic Entropy in the Thermopower Signals in Nanoribbons of the Magnetic Weyl Semimetal Co3Sn2S2.

Weyl semimetals exhibit interesting electronic properties due to their topological band structure. In particular, large anomalous Hall and anomalous Nernst signals are often reported, which allow for a detailed and quantitative study of subtle features. We pattern single crystals of the magnetic Weyl semimetal Co3Sn2S2 into nanoribbon devices using focused ion beam cutting and optical lithography. This approach enables a very precise study of the galvano- and thermomagnetic transport properties. Indeed, we found interesting features in the temperature dependency of the anomalous Hall and Nernst effects. We present an analysis of the data based on the Mott relation and identify in the Nernst response signatures of magnetic fluctuations enhancing the anomalous Nernst conductivity at the magnetic phase transition.

A Dinuclear Mechanism Implicated in Controlled Carbene Polymerization.

Carbene polymerization provides polyolefins that cannot be readily prepared from olefin monomers; however, controlled and living carbene polymerization has been a long-standing challenge. Here we report a new class of initiators, (π-allyl)palladium carboxylate dimers, which polymerize ethyl diazoacetate, a carbene precursor in a controlled and quasi-living manner, with nearly quantitative yields, degrees of polymerization >100, molecular weight dispersities 1.2-1.4, and well-defined, diversifiable chain ends. This method also provides block copolycarbenes that undergo microphase segregation. Experimental and theoretical mechanistic analysis supports a new dinuclear mechanism for this process.

All Electrical Access to Topological Transport Features in Mn1.8PtSn Films.

The presence of nontrivial magnetic topology can give rise to nonvanishing scalar spin chirality and consequently a topological Hall or Nernst effect. In turn, topological transport signals can serve as indicators for topological spin structures. This is particularly important in thin films or nanopatterned materials where the spin structure is not readily accessible. Conventionally, the topological response is determined by combining magnetotransport data with an independent magnetometry experiment. This approach is prone to introduce measurement artifacts. In this study, we report the observation of large topological Hall and Nernst effects in micropatterned thin films of Mn1.8PtSn below the spin reorientation temperature TSR ≈ 190 K. The magnitude of the topological Hall effect ρ xyT = 8 nΩm is close to the value reported in bulk Mn2PtSn, and the topological Nernst effect S xyT = 115 nV K-1 measured in the same microstructure has a similar magnitude as reported for bulk MnGe ( S xyT ∼ 150 nV K-1), the only other material where a topological Nernst was reported. We use our data as a model system to introduce a topological quantity, which allows one to detect the presence of topological transport effects without the need for independent magnetometry data. Our approach thus enables the study of topological transport also in nanopatterned materials without detrimental magnetization related limitations.

Mechanistically Guided Design of Ligands That Significantly Improve the Efficiency of CuH-Catalyzed Hydroamination Reactions.

Using a mechanically guided ligand design approach, a new ligand (SEGFAST) for the CuH-catalyzed hydroamination reaction of unactivated terminal olefins has been developed, providing a 62-fold rate increase over reactions compared to DTBM-SEGPHOS, the previous optimal ligand. Combining the respective strengths of computational chemistry and experimental kinetic measurements, we were able to quickly identify potential modifications that lead to more effective ligands, thus avoiding synthesizing and testing a large library of ligands. By optimizing the combination of attractive, noncovalent ligand-substrate interactions and the stability of the catalyst under the reaction conditions, we were able to identify a finely tuned hybrid ligand that greatly enables accelerated hydrocupration rates with unactivated alkenes. Moreover, a modular and robust synthetic sequence was devised, which allowed for the practical, gram-scale synthesis of these novel hybrid ligand structures.

Two-Step Magnetization Reversal FORC Fingerprint of Coupled Bi-Segmented Ni/Co Magnetic Nanowire Arrays.

First Order Reversal Curve (FORC) analysis has been established as an appropriate method to investigate the magnetic interactions among complex ferromagnetic nanostructures. In this work, the magnetization reversal mechanism of bi-segmented nanowires composed by long Co and Ni segments contacted at one side was investigated, as a model system to identify and understand the FORC fingerprint of a two-step magnetization reversal process. The resulting hysteresis loop of the bi-segmented nanowire array exhibits a completely different magnetic behavior than the one expected for the magnetization reversal process corresponding to each respective Co and Ni nanowire arrays, individually. Based on the FORC analysis, two possible magnetization reversal processes can be distinguished as a consequence of the ferromagnetic coupling at the interface between the Ni and Co segments. Depending on the relative difference between the magnetization switching fields of each segment, the softer magnetic phase induces the switching of the harder one through the injection and propagation of a magnetic domain wall when both switching fields are comparable. On the other hand, if the switching fields values differ enough, the antiparallel magnetic configuration of nanowires is also possible but energetically unfavorable, thus resulting in an unstable magnetic configuration. Making use of the different temperature dependence of the magnetic properties for each nanowire segment with different composition, one of the two types of magnetization reversal is favored, as demonstrated by FORC analyses.

Elucidating the Role of the Boronic Esters in the Suzuki-Miyaura Reaction: Structural, Kinetic, and Computational Investigations.

The Suzuki-Miyaura reaction is the most practiced palladium-catalyzed, cross-coupling reaction because of its broad applicability, low toxicity of the metal (B), and the wide variety of commercially available boron substrates. A wide variety of boronic acids and esters, each with different properties, have been developed for this process. Despite the popularity of the Suzuki-Miyaura reaction, the precise manner in which the organic fragment is transferred from boron to palladium has remained elusive for these reagents. Herein, we report the observation and characterization of pretransmetalation intermediates generated from a variety of commonly employed boronic esters. The ability to confirm the intermediacy of pretransmetalation intermediates provided the opportunity to clarify mechanistic aspects of the transfer of the organic moiety from boron to palladium in the key transmetalation step. A series of structural, kinetic, and computational investigations revealed that boronic esters can transmetalate directly without prior hydrolysis. Furthermore, depending on the boronic ester employed, significant rate enhancements for the transfer of the B-aryl groups were observed. Overall, two critical features were identified that enable the transfer of the organic fragment from boron to palladium: (1) the ability to create an empty coordination site on the palladium atom and (2) the nucleophilic character of the ipso carbon bound to boron. Both of these features ultimately relate to the electron density of the oxygen atoms in the boronic ester.

Technical feasibility study for production of tailored multielectrode arrays and patterning of arranged neuronal networks.

In this manuscript, we first reveal a simple ultra violet laser lithographic method to design and produce plain tailored multielectrode arrays. Secondly, we use the same lithographic setup for surface patterning to enable controlled attachment of primary neuronal cells and help neurite guidance. For multielectrode array production, we used flat borosilicate glass directly structured with the laser lithography system. The multi layered electrode system consists of a layer of titanium coated with a layer of di-titanium nitride. Finally, these electrodes are covered with silicon nitride for insulation. The quality of the custom made multielectrode arrays was investigated by light microscopy, electron microscopy and X-ray diffraction. The performance was verified by the detection of action potentials of primary neurons. The electrical noise of the custom-made MEA was equal to commercially available multielectrode arrays. Additionally, we demonstrated that structured coating with poly lysine, obtained with the aid of the same lithographic system, could be used to attach and guide neurons to designed structures. The process of neuron attachment and neurite guidance was investigated by light microscopy and charged particle microscopy. Importantly, the utilization of the same lithographic system for MEA fabrication and poly lysine structuring will make it easy to align the architecture of the neuronal network to the arrangement of the MEA electrode.. In future studies, this will lead to multielectrode arrays, which are able to specifically attach neuronal cell bodies to their chemically defined electrodes and guide their neurites, gaining a controlled connectivity in the neuronal network. This type of multielectrode array would be able to precisely assign a signal to a certain neuron resulting in an efficient way for analyzing the maturation of the neuronal connectivity in small neuronal networks.

Does Sodium Citrate Cause the Same Ergogenic Effect As Sodium Bicarbonate on Swimming Performance?

The aim of this study was to investigate the effect of ingesting sodium bicarbonate (SB) and sodium citrate (SC) on 400 m high-intensity swimming performance and blood responses. Six nationally ranked male swimmers (20.7 ± 2.1 yrs; 184 ± 6 cm; 79.9 ± 3.9 kg; 10.6 ± 1% body fat) participated in a double blinded, placebo controlled crossover trial. Ninety minutes after consuming SB (0.3 g·kg-1), SC (0.3 g·kg-1) or a placebo (PL) participants completed a single 400-m freestyle maximal test on three consecutive days. The order of the supplementation was randomized. Capillary blood samples were collected on 4 occasions: at rest (baseline), 60 min post-ingestion, immediately post-trial and 15 min post-trial. Blood pH, HCO3- concentration and base excess (BE) were determined. Blood pH, HCO3-, BE were significantly elevated from before loading to the pre-test (60 min post-ingestion) (p < 0.05) after SB ingestion, but not after SC ingestion (p > 0.05). Performance times were improved by 0.6% (p > 0.05) after supplementation of SB over PL in 5 out of 6 participants (responders). In contrast, ingestion of SC decreased performance by 0.2% (p > 0.05). No side effects were observed in either trial. Delayed blood response was observed after SC ingestion compared to SB and this provided no or modest ergogenic effect, respectively, for single bout high-intensity swimming exercise. Monitoring the magnitude of the time-to-peak level rise in alkalosis may be recommended in order to individualize the loading time accordingly before commencement of exercise.

Large magneto-Seebeck effect in magnetic tunnel junctions with half-metallic Heusler electrodes.

Spin caloritronics studies the interplay between charge-, heat- and spin-currents, which are initiated by temperature gradients in magnetic nanostructures. A plethora of new phenomena has been discovered that promises, e.g., to make wasted heat in electronic devices useable or to provide new read-out mechanisms for information. However, only few materials have been studied so far with Seebeck voltages of only some microvolt, which hampers applications. Here, we demonstrate that half-metallic Heusler compounds are hot candidates for enhancing spin-dependent thermoelectric effects. This becomes evident when considering the asymmetry of the spin-split density of electronic states around the Fermi level that determines the spin-dependent thermoelectric transport in magnetic tunnel junctions. We identify Co2FeAl and Co2FeSi Heusler compounds as ideal due to their energy gaps in the minority density of states, and demonstrate devices with substantially larger Seebeck voltages and tunnel magneto-Seebeck effect ratios than the commonly used Co-Fe-B-based junctions.

A study of the beam-specific interplay effect in proton pencil beam scanning delivery in lung cancer.

BACKGROUND: For lung tumors with large motion amplitudes, the use of proton pencil beam scanning (PBS) can produce large dose errors. In this study, we assess under what circumstances PBS can be used to treat lung cancer patients who exhibit large tumor motion, based on the quantification of tumor motion and the dose interplay. MATERIAL AND METHODS: PBS plans were optimized on average 4DCT datasets using a beam-specific PTV method for 10 consecutive patients with locally advanced non-small-cell-lung-cancer (NSCLC) treated with proton therapy to 6660/180 cGy. End inhalation (CT0) and end exhalation (CT50) were selected as the two extreme scenarios to acquire the relative stopping power ratio difference (Δrsp) for a respiration cycle. The water equivalent difference (ΔWET) per radiological path was calculated from the surface of patient to the iCTV by integrating the Δrsp of each voxel. The magnitude of motion of voxels within the target follows a quasi-Gaussian distribution. A motion index (MI (>5mm WET)), defined as the percentage of target voxels with an absolute integral ΔWET larger than 5 mm, was adopted as a metric to characterize interplay. To simulate the treatment process, 4D dose was calculated by accumulating the spot dose on the corresponding respiration phase to the reference phase CT50 by deformable image registration based on spot timing and patient breathing phase. RESULTS: The study indicated that the magnitude of target underdose in a single fraction plan is proportional to the MI (p < .001), with larger motion equating to greater dose degradation and standard deviations. The target homogeneity, minimum, maximum and mean dose in the 4D dose accumulations of 37 fractions varied as a function of MI. CONCLUSIONS: This study demonstrated that MI can predict the level of dose degradation, which potentially serves as a clinical decision tool to assess whether lung cancer patients are potentially suitable to receive PBS treatment.

Structural, Kinetic, and Computational Characterization of the Elusive Arylpalladium(II)boronate Complexes in the Suzuki-Miyaura Reaction.

The existence of the oft-invoked intermediates containing the crucial Pd-O-B subunit, the "missing link", has been established in the Suzuki-Miyaura cross-coupling reaction. The use of low-temperature, rapid injection NMR spectroscopy (RI-NMR), kinetic studies, and computational analysis has enabled the generation, observation, and characterization of these highly elusive species. The ability to confirm the intermediacy of Pd-O-B-containing species provided the opportunity to clarify mechanistic aspects of the transfer of the organic moiety from boron to palladium in the key transmetalation step. Specifically, these studies establish the identity of two different intermediates containing Pd-O-B linkages, a tri-coordinate (6-B-3) boronic acid complex and a tetra-coordinate (8-B-4) boronate complex, both of which undergo transmetalation leading to the cross-coupling product. Two distinct mechanistic pathways have been elucidated for stoichiometric reactions of these complexes: (1) transmetalation via an unactivated 6-B-3 intermediate that dominates in the presence of an excess of ligand, and (2) transmetalation via an activated 8-B-4 intermediate that takes place with a deficiency of ligand.

Pre-transmetalation intermediates in the Suzuki-Miyaura reaction revealed: The missing link.

Despite the widespread application of Suzuki-Miyaura cross-coupling to forge carbon-carbon bonds, the structure of the reactive intermediates underlying the key transmetalation step from the boron reagent to the palladium catalyst remains uncertain. Here we report the use of low-temperature rapid injection nuclear magnetic resonance spectroscopy and kinetic studies to generate, observe, and characterize these previously elusive complexes. Specifically, this work establishes the identity of three different species containing palladium-oxygen-boron linkages, a tricoordinate boronic acid complex, and two tetracoordinate boronate complexes with 2:1 and 1:1 stoichiometry with respect to palladium. All of these species transfer their boron-bearing aryl groups to a coordinatively unsaturated palladium center in the critical transmetalation event.

Case Study: Competition Nutrition Intakes During the Open Water Swimming Grand Prix Races in Elite Female Swimmer.

The nutritional intake of elite open water swimmers during competition is not well established, and therefore this case study aims to provide new insights by describing the feeding strategies adopted by an elite female swimmer (28 yrs; height; 1.71 m; body mass: 60 kg; body fat: 16.0%) in the FINA open water Grand Prix 2014.Seven events of varying distances (15-88 km) and durations (3-12 hrs) were included. In all events, except one, feeds were provided from support boats. Swimmer and support staff were instructed to track in detail all foods and beverages consumed during the events. Nutritional information was gathered from the packaging and dietary supplements labels and analyzed by nutrition software. Mean carbohydrate (CHO) and protein intake reached 83 ± 5 g·h-1 and 12 ± 8 g·h-1, respectively. Fat intake was neglected (~1 g·h-1). Mean in-race energy intake reached 394 ± 26 kcal·h-1. Dietary supplements in the form of sport beverages and gels, containing multitransportable CHO, provided 40 ± 4 and 49 ± 6% of all CHO energy, respectively. Caffeine (3.6 ± 1.8 mg·kg-1 per event) and sodium (423 ± 16 mg·h-1) were additionally supplemented in all events. It was established that continuous intake of high doses of CHO and sodium and moderate dose of caffeine were an essential part of the feeding strategy for elite-level high intensity ultra-endurance open-water swimming races. A well scheduled and well-prepared nutrition strategy is believed to have ensured optimal individual performance during Grand Prix events.