Novel Cβ–Cγ Bond Cleavages of Tryptophan-Containing Peptide Radical Cations

In this study, we observed unprecedented cleavages of the Cβ–Cγ bonds of tryptophan residue side chains in a series of hydrogen-deficient tryptophan-containing peptide radical cations (M•+) during low-energy collision-induced dissociation (CID). We used CID experiments and theoretical density functional theory (DFT) calculations to study the mechanism of this bond cleavage, which forms [M – 116]+ ions. The formation of an α-carbon radical intermediate at the tryptophan residue for the subsequent Cβ–Cγ bond cleavage is analogous to that occurring at leucine residues, producing the same product ions; this hypothesis was supported by the identical product ion spectra of [LGGGH – 43]+ and [WGGGH – 116]+, obtained from the CID of [LGGGH]•+ and [WGGGH]•+, respectively. Elimination of the neutral 116-Da radical requires inevitable dehydrogenation of the indole nitrogen atom, leaving the radical centered formally on the indole nitrogen atom ([Ind]•-2), in agreement with the CID data for [WGGGH]•+ and [W1-CH3GGGH]•+; replacing the tryptophan residue with a 1-methyltryptophan residue results in a change of the base peak from that arising from a neutral radical loss (116 Da) to that arising from a molecule loss (131 Da), both originating from Cβ–Cγ bond cleavage. Hydrogen atom transfer or proton transfer to the γ-carbon atom of the tryptophan residue weakens the Cβ–Cγ bond and, therefore, decreases the dissociation energy barrier dramatically

A systematic review of tests of empathy in medicine

Abstract Background Empathy is frequently cited as an important attribute in physicians and some groups have expressed a desire to measure empathy either at selection for medical school or during medical (or postgraduate) training. In order to do this, a reliable and valid test of empathy is required. The purpose of this systematic review is to determine the reliability and validity of existing tests for the assessment of medical empathy. Methods A systematic review of research papers relating to the reliability and validity of tests of empathy in medical students and doctors. Journal databases (Medline, EMBASE, and PsycINFO) were searched for English-language articles relating to the assessment of empathy and related constructs in applicants to medical school, medical students, and doctors. Results From 1147 citations, we identified 50 relevant papers describing 36 different instruments of empathy measurement. As some papers assessed more than one instrument, there were 59 instrument assessments. 20 of these involved only medical students, 30 involved only practising clinicians, and three involved only medical school applicants. Four assessments involved both medical students and practising clinicians, and two studies involved both medical school applicants and students. Eight instruments demonstrated evidence of reliability, internal consistency, and validity. Of these, six were self-rated measures, one was a patient-rated measure, and one was an observer-rated measure. Conclusion A number of empathy measures available have been psychometrically assessed for research use among medical students and practising medical doctors. No empathy measures were found with sufficient evidence of predictive validity for use as selection measures for medical school. However, measures with a sufficient evidential base to support their use as tools for investigating the role of empathy in medical training and clinical care are available.</p

Benchmarking of trauma care worldwide: the potential value of an International Trauma Data Bank (ITDB)

Background: National trauma registries have helped improve patient outcomes across the world. Recently, the idea of an International Trauma Data Bank (ITDB) has been suggested to establish global comparative assessments of trauma outcomes. The objective of this study was to determine whether global trauma data could be combined to perform international outcomes benchmarkingMethods: We used observed/expected (O/E) mortality ratios to compare two trauma centers [European high-income country (HIC) and Asian lower-middle income country (LMIC)] with centers in the North American National Trauma Data Bank (NTDB). Patients (≥16 years) with blunt/penetrating injuries were included. Multivariable logistic regression, adjusting for known predictors of trauma mortality, was performed. Estimates were used to predict the expected deaths at each center and to calculate O/E mortality ratios for benchmarking. Results: A total of 375,433 patients from 301 centers were included from the NTDB (2002–2010). The LMIC trauma center had 806 patients (2002–2010), whereas the HIC reported 1,003 patients (2002–2004). The most important known predictors of trauma mortality were adequately recorded in all datasets. Mortality benchmarking revealed that the HIC center performed similarly to the NTDB centers [O/E = 1.11 (95 % confidence interval (CI) 0.92–1.35)], whereas the LMIC center showed significantly worse survival [O/E = 1.52 (1.23–1.88)]. Subset analyses of patients with blunt or penetrating injury showed similar results.Conclusions: Using only a few key covariates, aggregated global trauma data can be used to adequately perform international trauma center benchmarking. The creation of the ITDB is feasible and recommended as it may be a pivotal step towards improving global trauma outcomes. This work was declared as the best oral presentation at the International Association for Trauma Surgery and Intensive Care/the American Association for the Surgery of Trauma (IATSIC/AAST) Scientific Paper Session at the International Surgical Week (ISW) 2013, Helsinki, Finland