In situ generation of Mes2Mg as a non-nucleophilic carbon-centred base reagent for the efficient one-pot conversion of ketones to silyl enol ethers

Treatment of commercially available MesMgBr with 1,4-dioxane produces the key Mes2Mg reagent in situ which then mediates the deprotonation of ketones to deliver trimethylsilyl enol ethers, at readily accessible temperatures and without any nucleophilic addition, in an expedient and high yielding one-pot process

String universality in ten dimensions

We show that the ${\cal N}=1$ supergravity theories in ten dimensions with gauge groups $U(1)^{496}$ and $E_8 \times U(1)^{248}$ are not consistent quantum theories. Cancellation of anomalies cannot be made compatible with supersymmetry and abelian gauge invariance. Thus, in ten dimensions all supersymmetric theories of gravity without known inconsistencies are realized in string theory.Comment: 7 pages, 1 figure, LaTeX. v2: typos corrected on version appearing in PR

Abdominal functional electrical stimulation to enhance mechanical insufflation-exsufflation

Context: Respiratory complications, attributed to the build-up of secretions in the airway, are a leading cause of rehospitalisation for the tetraplegic population. Previously, we observed that the application of Abdominal Functional Electrical Stimulation (AFES) improved cough function and increased demand for secretion removal, suggesting AFES may aid secretion clearance. Clinically, secretion clearance is commonly achieved by using Mechanical insufflation-exsufflation (MI-E) to simulate a cough. In this study the feasibility of combining AFES with MI-E is evaluated. Findings: AFES was successfully combined with MI-E at eight fortnightly assessment sessions conducted with one sub-acute participant with tetraplegia. By using the signal from a pressure sensor, integrated with the MI-E device, AFES was correctly applied in synchrony with MI-E with an accuracy of 96.7%. Acute increases in exhaled volume and peak flow were observed during AFES assisted MI-E, compared to MI-E alone, at six of eight assessment sessions. Conclusion: The successful integration of AFES with MI-E at eight assessment sessions demonstrates the feasibility of this technique. The acute increases in respiratory function observed at the majority of assessment sessions generate the hypothesis that AFES assisted MI-E may be more effective for secretion clearance than MI-E alone

The problem with problems : fundamental to applied research using palladium

The studies are very grateful for the support we have received from the following sources for the chemistry described in this Account: EPSRC (EP/R025754/1), The Leverhulme Trust (RPG-2015-308), and GlaxoSmithKline and AstraZeneca for several CASE awards and iCASE studentships.This Account describes the development of our cross-coupling and medicinal chemistry research from its origins at the outset of my independent career through to the present day. Throughout, the decisions and motivations as well as the mistakes and pitfalls are discussed.Publisher PDFPeer reviewe

Electro-optic techniques for longitudinal electron bunch diagnostics

Electro-optic techniques are becoming increasingly important in ultrafast electron bunch longitudinal diagnostics and have been successfully implemented at various accelerator laboratories. The longitudinal bunch shape is directly obtained from a single-shot, non-intrusive measurement of the temporal electric field profile of the bunch. Further- more, the same electro-optic techniques can be used to measure the temporal profile of terahertz / far-infrared opti- cal pulses generated by a CTR screen, at a bending magnet (CSR), or by an FEL. This contribution summarizes the re- sults obtained at FELIX and FLASH

Abdominal functional electrical stimulation to assist ventilator weaning in acute tetraplegia: a cohort study

Background Severe impairment of the major respiratory muscles resulting from tetraplegia reduces respiratory function, causing many people with tetraplegia to require mechanical ventilation during the acute stage of injury. Abdominal Functional Electrical Stimulation (AFES) can improve respiratory function in non-ventilated patients with sub-acute and chronic tetraplegia. The aim of this study was to investigate the clinical feasibility of using an AFES training program to improve respiratory function and assist ventilator weaning in acute tetraplegia.<p></p> Methods AFES was applied for between 20 and 40 minutes per day, five times per week on four alternate weeks, with 10 acute ventilator dependent tetraplegic participants. Each participant was matched retrospectively with a ventilator dependent tetraplegic control, based on injury level, age and sex. Tidal Volume (VT) and Vital Capacity (VC) were measured weekly, with weaning progress compared to the controls.<p></p> Results Compliance to training sessions was 96.7%. Stimulated VT was significantly greater than unstimulated VT. VT and VC increased throughout the study, with mean VC increasing significantly (VT: 6.2 mL/kg to 7.8 mL/kg VC: 12.6 mL/kg to 18.7 mL/kg). Intervention participants weaned from mechanical ventilation on average 11 (sd: ± 23) days faster than their matched controls.<p></p> Conclusion The results of this study indicate that AFES is a clinically feasible technique for acute ventilator dependent tetraplegic patients and that this intervention may improve respiratory function and enable faster weaning from mechanical ventilation.<p></p&gt

Ni vs. Pd in Suzuki-Miyaura sp2-sp2 cross-coupling : a head-to-head study in a comparable precatalyst/ligand system

We thank the University of St Andrews for a PhD studentship (MJW).The Suzuki-Miyaura reaction is a cornerstone method for sp2-sp2 cross-coupling in industry. There has been a concerted effort to enable the use of Ni catalysis as an alternative to Pd in order to mitigate cost and improve sustainability. Despite significant advances, ligand development for Ni-catalyzed Suzuki-Miyaura cross-coupling remains underdeveloped when compared to Pd and, as a consequence, ligands for Ni-catalyzed processes are typically taken from the Pd arena. In this study we evaluate the effect of using a similar Ni and Pd precatalyst based on a common bidentate ligand (dppf) in a head-to-head format for the most common type of biaryl couplings, establishing the practical implications of direct replacement of Pd with Ni, and identifying the potential origins of these observations in a mechanistic context.PostprintPeer reviewe

Single shot longitudinal bunch profile measurements by temporally resolved electro-optical detection

For the high gain operation of a SASE FEL, extremely short electron bunches are essential to generate sufficiently high peak currents. At the superconducting linac of FLASH at DESY, we have installed an electro- optic measurement system to probe the time structure of the electric field of single ~100 fs electron bunches. In this technique, the field induced birefringence in an electro-optic crystal is encoded on a chirped picosecond laser pulse. The longitudinal electric field profile of the electron bunch is then obtained from the encoded optical pulse by a single shot cross correlation with a 35 fs laser pulse using a second harmonic crystal (temporal decoding). An electro-optical signal exhibiting a feature with 118 fs FWHM was observed, and this is close to the limit of resolution due to the material properties of the particular electro-optic crystal used. The measured electro-optic signals are compared to bunch shapes simultaneously measured with a transverse deflecting cavity

Benchmarking of electro-optic monitors for femtosecond electron bunches

The longitudinal profiles of ultrashort relativistic electron bunches at the soft x-ray free-electron laser FLASH have been investigated using two single-shot detection schemes: an electro-optic (EO) detector measuring the Coulomb field of the bunch and a radio-frequency structure transforming the charge distribution into a transverse streak. A comparison permits an absolute calibration of the EO technique. EO signals as short as 60 fs (rms) have been observed, which is a new record in the EO detection of single electron bunches and close to the limit given by the EO material properties

An alternative synthesis of cycloalkyl-substituted CPA catalysts and application in asymmetric protonation reactions

LAM thanks the EPSRC (grant number EP/S027165/1) for postdoctoral funding.An alternative synthesis of cycloalkyl-substituted CPA catalysts is reported. A Negishi coupling offers improved yields and purity of the necessary 1,3,5-tri(cycloalkyl)benzenes. Limitations in the use of commercial organozinc reagents have been identified and a robust procedure for the preparation of these reagents is detailed. Similarly, a robust procedure for the key Kumada coupling is also provided. The route is demonstrated by preparation of three different tri(cycloalkyl)aryl-substituted CPAs and the utility of these catalysts in asymmetric protonation reactions is shown.Publisher PDFPeer reviewe