Ligand Exchange/Scrambling Study of Gold(I)-Phosphine Complexes in the Solid Phase by DESI-MS Analysis.

Only a few analytical techniques are available for the characterization of mechanochemical synthetic reaction products. We demonstrate here that DESI-MS is a powerful technique for this purpose, combining the selectivity of MS-based assays with the simplicity and in situ analysis capability of ambient ionization methods. In this work, we report that auranofin, a gold-based drug, and its precursor triethylphosphine gold(I) chloride undergo a complex array of ligand exchange/scrambling reactions with thiol-containing amino acids in the solid state. The products were readily characterized by DESI-MS analysis from the solid-phase reaction, clearly exhibiting ligand exchange and scrambling, with independent confirmation by solid state 13C-NMR. The thioglucose and triethylphosphine moieties exchanged with cysteine and its derivatives, whereas the glutathione replaced 2,3,4,6-tetra-o-acetyl-ß-1-D-glucopyranose only. It was concluded that ligand exchange and scrambling reactions can be carried out in the solid state, and some of the unique products reported in this study can be conveniently prepared through mechanochemical synthesis in good yields (> 98%), as demonstrated by synthesis of (L-cysteinato-S)-triethylphosphine gold(I) from triethylphosphine gold(I) chloride and L-cysteine.

Visceral Vistas: Basil Hirschowitz and the Birth of Fiberoptic Endoscopy.

Fiberoptic endoscopy was developed at the University of Michigan in the 1950s by gastroenterology fellow Basil Hirschowitz and 2 physicists. Previous methods to visualize the gastrointestinal lumen used rigid instruments that relied on rudimentary optical systems. They were limited in reach and caused patients considerable discomfort. Fiberoptic technology dramatically changed endoscopic practice. The fiberoptic endoscope, or fiberscope, was a flexible instrument that allowed direct inspection of the gastrointestinal lumen. Although many practicing endoscopists initially resisted its adoption, the fiberscope ultimately held sway. Studying the period from the fiberscope's first introduction in the late 1950s to its more widespread acceptance in the late 1960s may help us understand how a new technology makes its way into routine clinical practice.

Rural experience for junior doctors: is it time to make it mandatory?

OBJECTIVE: To determine whether rural practice terms for junior doctors result in increased interest in rural practice and whether these terms improve learning experiences, clinical skills and insight into difficulties of rural practice. DESIGN: Semistructured, self-administered survey with questions on respondent demographics, clinical experience during rural practice terms, post-rural experience and personal opinion. SETTING: South East Queensland. PARTICIPANTS: Thirty junior doctors from three tertiary hospitals were approached. The response rate was 100%. MAIN OUTCOME MEASURES: Exploration of junior doctors' rural term experience. RESULTS: Two thirds (67%) of the respondents reported feeling uncomfortable with respect to clinical practice requirements during their rural terms. Half (47%) performed procedures they had only previously performed in simulation environments, and the majority (87%) relied on textbooks or other resources on a daily basis. Two thirds (67%) changed aspects of their usual clinical practice while practising in a rural setting, and 80% reported a change in attitude towards the hardships faced by rural practitioners. The majority of the respondents (87%) enjoyed their rural term, gaining confidence as a result of it, and more than half (53%) reported considering working in rural areas in the future. CONCLUSIONS: The results of this survey suggest that junior doctors on rural rotations are required to perform at a clinical level higher than that required of them in metropolitan hospitals. While their clinical experience appears to result in a greater interest in future rural career possibilities for junior doctors, this survey highlights the requirement to improve support for junior doctors undertaking terms in rural areas.

Options for postgraduate anatomy education in Australia and New Zealand.

AIMS: Medical education in Australia has changed considerably in recent times. As a result, hours dedicated to subjects such as anatomy have been reduced. Young doctors preparing for a career in anatomy-focussed specialties such as surgery and radiology require an indepth knowledge of this subject matter. Many Australian and New Zealand universities now offer postgraduate anatomy courses to address this potential gap in a budding surgeon's education. This article summarises the current options for postgraduate surgical anatomy education in Australia and New Zealand. METHODS: All universities in Australia and New Zealand were contacted between September 2010 and December 2010 regarding the nature and content of course offerings. An Internet-based search was also conducted. RESULTS: There are currently nine universities in Australia and New Zealand offering postgraduate anatomy courses. Courses vary in contact hours, dissection time, lecture content, and examination methods. There are currently two universities offering a Postgraduate Diploma of Surgical Anatomy - the University of Melbourne, and the University of Otago. University of Western Australia and the University of New England offer a graduate diploma and a graduate certificate, respectively. Several other universities offer courses that deliver quality anatomical education but do not award students a university-recognised qualification. The Australian Orthopaedic Association now offers courses in Perth, Sydney and Brisbane, which delivers anatomy education specific to orthopaedics. CONCLUSIONS: There are a number of courses available to budding surgeons and radiologists to help fill the anatomy education void. With the development of such courses questions of accessibility, affordability and equity remain.

Direct detection of pharmaceuticals and personal care products from aqueous samples with thermally-assisted desorption electrospray ionization mass spectrometry.

An ambient mass spectrometric method based on desorption electrospray ionization (DESI) has been developed to allow rapid, direct analysis of contaminated water samples, and the technique was evaluated through analysis of a wide array of pharmaceutical and personal care product (PPCP) contaminants. Incorporating direct infusion of aqueous sample and thermal assistance into the source design has allowed low ppt detection limits for the target analytes in drinking water matrices. With this methodology, mass spectral information can be collected in less than 1 min, consuming ~100 µL of total sample. Quantitative ability was also demonstrated without the use of an internal standard, yielding decent linearity and reproducibility. Initial results suggest that this source configuration is resistant to carryover effects and robust towards multi-component samples. The rapid, continuous analysis afforded by this method offers advantages in terms of sample analysis time and throughput over traditional hyphenated mass spectrometric techniques.