High-Energy-Density Material with Magnetically Modulated Ignition.

Preparation of a redox-frustrated high-energy-density energetic material is achieved by gentle protolysis of Mn[N(SiMe)] with the perchlorate salt of the tetrazolamide [HNBuMeTz]ClO (Tz = tetrazole), yielding the MnN hexagonal prismatic cluster, Mn(μ-NTzBuMe)(ClO). Quantum mechanics-based molecular dynamics simulations of the decomposition of this molecule predict that magnetic ordering of the Mn ions influences the pathway and rates of decomposition, suggesting that the initiation of decomposition of the bulk material might be significantly retarded by an applied magnetic field. We report here experimental tests of the prediction showing that the presence of a 0.

Domino Michael/Mannich Annulation Reaction of -Sulfinyl Lithiodienamines.

The domino Michael/Mannich (DMM) annulation reaction between an -sulfinyl lithiodienamine and an electrophilic alkene is developed for the synthesis of chiral 2-amino cyclohexenes, a key building block in asymmetric synthesis. The DMM reaction proceeds at low temperature while maintaining the stereochemical fidelity. The product functionalized amino cyclohexenes, here obtained in 55-82% yield with diastereomeric ratios as high as >19:1.

A tool to evaluate proportionality and necessity in the use of restrictive practices in forensic mental health settings: the DRILL tool (Dundrum restriction, intrusion and liberty ladders).

Background: Prevention of violence due to severe mental disorders in psychiatric hospitals may require intrusive, restrictive and coercive therapeutic practices. Research concerning appropriate use of such interventions is limited by lack of a system for description and measurement. We set out to devise and validate a tool for clinicians and secure hospitals to assess necessity and proportionality between imminent violence and restrictive practices including de-escalation, seclusion, restraint, forced medication and others.

Quality improvement in forensic mental health: the East London forensic violence reduction collaborative.

Ward-based violence is the most significant cause of reported safety incidents at East London NHS Foundation Trust (ELFT). It impacts on patient and staff safety, well-being, clinical care and the broader hospital community in various direct and indirect ways. The contributing factors are varied and complex.

Properties and Promise of Catenated Nitrogen Systems As High-Energy-Density Materials.

The properties of catenated nitrogen molecules, molecules containing internal chains of bonded nitrogen atoms, is of fundamental scientific interest in chemical structure and bonding, as nitrogen is uniquely situated in the periodic table to form kinetically stable compounds often with chemically stable N-N bonds but which are thermodynamically unstable in that the formation of stable multiply bonded N is usually thermodynamically preferable. This unique placement in the periodic table makes catenated nitrogen compounds of interest for development of high-energy-density materials, including explosives for defense and construction purposes, as well as propellants for missile propulsion and for space exploration. This review, designed for a chemical audience, describes foundational subjects, methods, and metrics relevant to the energetic materials community and provides an overview of important classes of catenated nitrogen compounds ranging from theoretical investigation of hypothetical molecules to the practical application of real-world energetic materials.

Activation of C-H, N-H, and O-H Bonds via Proton-Coupled Electron Transfer to a Mn(III) Complex of Redox-Noninnocent Octaazacyclotetradecadiene, a Catenated-Nitrogen Macrocyclic Ligand.

Reaction of 1,3-diazidopropane with an electron-rich Mn(II) precursor results in oxidation of the metal center to a Mn complex with concomitant assembly of the macrocyclic ligand into the 1,2,3,4,8,9,10,11-octaazacyclotetradeca-2,9-diene-1,4,8,11-tetraido (OIM) ligand. Although describable as a Werner Mn(V) complex, analysis by X-ray diffraction, magnetic measurements, X-ray photoelectron spectroscopy, cyclic voltammetry, and density functional theory calculations suggest an electronic structure consisting of a Mn(III) metal center with a noninnocent OIM diradical ligand. The resulting complex, (OIM)Mn(NH Bu), reacts via proton-coupled electron transfer (PCET) with phenols to form phenoxyl radicals, with dihydroanthracene to form anthracene, and with (2,4-di tert-butyltetrazolium-5-yl)amide to extrude a tetrazyl radical.

Manganese-Mediated Linkage of Perchlorate to Aminotetrazoles Produces Twice the Energy Density of the Unmetalated Salt.

New regimes of energy density in energetic materials may be achieved by replacement of oxidizing nitro groups with stronger oxidants such as oxychlorine species. We report the energetic material 1,3-di-tert-butyltetrazolium-5-imidoperchloratomanganese(II) 2, which crystallizes as an oligomeric cubane cluster. Bomb calorimetry on the amorphous, solvent-free phase gives an energy density of at least 40±3 MJ L , higher than hydrocarbon combustion in air, more than twice that of traditional energetic nitramines, and ≈70 % higher than that of the unmetalated tetrazolium perchlorate salt without metal linkage.

Improving clinical performance using rehearsal or warm-up: an advanced literature review of randomized and observational studies.

Purpose: To determine whether rehearsal (the deliberate practice of skills specific to a procedure) or warm-up (the act or process of warming up by light exercise or practice) prior to performing complex clinical procedures on patients can improve the task performance of operators and operating teams.

Method: The authors performed an advanced literature search for clinical studies published between 1975 and October 2012 using MEDLINE, EMBASE, the Cochrane Controlled Trials Register, ISI Web of Knowledge, and clinicaltrials.gov.

The effect of simulation-based training on initial performance of ultrasound-guided axillary brachial plexus blockade in a clinical setting - a pilot study.

Background: In preparing novice anesthesiologists to perform their first ultrasound-guided axillary brachial plexus blockade, we hypothesized that virtual reality simulation-based training offers an additional learning benefit over standard training. We carried out pilot testing of this hypothesis using a prospective, single blind, randomized controlled trial.

Methods: We planned to recruit 20 anesthesiologists who had no experience of performing ultrasound-guided regional anesthesia.

Determinants of learning ultrasound-guided axillary brachial plexus blockade.

Background And Objectives: Training in medical procedural skills is currently undergoing important change. We set out to identify those factors, perceived by trainers and trainees, to be important determinants of learning ultrasound-guided axillary brachial plexus blockade (USgABPB).

Methods: We performed a structured, prospective, qualitative analysis of these determinants using a design-based approach.

Proactive error analysis of ultrasound-guided axillary brachial plexus block performance.

Background: Detailed description of the tasks anesthetists undertake during the performance of a complex procedure, such as ultrasound-guided peripheral nerve blockade, allows elements that are vulnerable to human error to be identified. We have applied 3 task analysis tools to one such procedure, namely, ultrasound-guided axillary brachial plexus blockade, with the intention that the results may form a basis to enhance training and performance of the procedure.

Methods: A hierarchical task analysis of the procedure was performed with subsequent analysis using systematic human error reduction and prediction approach (SHERPA).

VR-based training and assessment in ultrasound-guided regional anesthesia: from error analysis to system design.

If VR-based medical training and assessment is to improve patient care and safety (i.e. a genuine health gain), it has to be based on clinically relevant measurement of performance.

Ultrasound-guided axillary brachial plexus block with 20 milliliters local anesthetic mixture versus general anesthesia for upper limb trauma surgery: an observer-blinded, prospective, randomized, controlled trial.

Objective: We performed a randomized, controlled trial comparing low-dose ultrasound-guided axillary block with general anesthesia evaluating anesthetic and perioperative analgesic outcomes.

Methods: Patients were randomized to either ultrasound-guided axillary block or general anesthesia. Ultrasound-guided axillary block was performed using a needle-out-of-plane approach.