Protoisomerization of indigo di- and monoimines.

Indigo di- and monoimines can be protonated to form stable salts in which the central C=C bond has isomerized from a trans to cis configuration. Deprotonation of these salts regenerates the neutral trans species. The protonation chemistry of indigo is also explored.

Promoting the management of acute upper gastrointestinal bleeds among junior doctors: a quality improvement project.

Though they are knowledgeable, foundation year one (FY1) doctors can lack skills and confidence in acute situations due to inexperience. This was witnessed when a new FY1 on call attended an acute upper gastrointestinal bleed (UGIB), a common emergency with a 10% in hospital mortality rate. We aimed to improve FY1s' ability to manage these critical patients through simulation based teaching, before and after the introduction of an algorithm summarising current guidelines. After assessing the FY1s' perceived level of confidence in managing UGIBs, they individually attended a simulation session which evaluated specific aspects of their assessment and management plans. Immediate debriefing and subsequent teaching sessions reinforced learning points, with an algorithm instituted as an aide mémoire to improve efficiency. A repeat simulation session assessed improvements in both subjective confidence and objective management targets. All FY1s expressed improved confidence in managing patients with UGIBs. There were improvements across the board in their assessment and management, notably: verbalisation of concern for hypotension increased to 100% (from 60%), two points of intravenous access requested in 100% of cases (from 53%), and a 76 second reduction in time to call for senior support. Collectively, these individual aspects led to improved patient care. Effective management of acute patients is best learnt through exposure, and simulation based teaching provides a safe but powerful modality to aid transition from textbook theory to ward situations. Algorithms can streamline care and hasten the stabilisation of patients. This project reinforces generic competencies that FY1s can translate to their management of not only UGIBs, but many acute presentations, providing a convincing argument for broader simulation use in FY1 teaching.

Lanthanide complexes of the Kläui metalloligand, CpCo(P═O(OR)2)3: an examination of ligand exchange kinetics between isotopomers by electrospray mass spectrometry.

A series of lanthanide complexes, {[CpCo(P═O(OR)2)3]2Ln(H2O)x}(+)Cl(-) (Ln = Nd, 3; Eu, 4; Tb, 5; Yb, 6; R = Et, a; R = Ph, b) bearing two cobalt metalloligands were prepared. Electrospray mass spectrometry and thermogravimetric analysis suggest that the cations are either solvent-free or contain very weakly bound water molecules. The related complex {[CpCo(P═O(OPh)2)3]2Yb}(+) [CoCl3(THF)](-), 7, was crystallographically characterized, and the cation in this case was confirmed to be 6-coordinate and solvent-free. Ligand exchange rates between the d0- and d60-isotopomers of 3a-6a and 5b were determined in acetonitrile by electrospray mass spectrometry. The ligand exchange rate was found to increase by almost 4 orders of magnitude from the smallest (Yb, 6a, k = 0.3 M(-1) s(-1)) to largest ion (Nd, 3a, >2500 M(-1) s(-1)) in acetonitrile. Additionally, the ligand exchange rate increased rapidly for 5a (Tb) with increasing water concentration from 30 M(-1) s(-1) in pure acetonitrile to 268 M(-1) s(-1) in 50:50 (v/v) acetonitrile/water. Changing the phosphite substituent had no significant impact on the rate of ligand exchange for 5b (R = Ph) relative to 5a (R = Et).