Novel Mass Spectrometric Analysis Methods for Anabolic Androgenic Steroids in Sports Drug Testing

The feasibility of different modern analytical techniques for the mass spectrometric detection of anabolic androgenic steroids (AAS) in human urine was examined in order to enhance the prevalent analytics and to find reasonable strategies for effective sports drug testing. A comparative study of the sensitivity and specificity between gas chromatography (GC) combined with low (LRMS) and high resolution mass spectrometry (HRMS) in screening of AAS was carried out with four metabolites of methandienone. Measurements were done in selected ion monitoring mode with HRMS using a mass resolution of 5000. With HRMS the detection limits were considerably lower than with LRMS, enabling detection of steroids at low 0.2-0.5 ng/ml levels. However, also with HRMS, the biological background hampered the detection of some steroids. The applicability of liquid-phase microextraction (LPME) was studied with metabolites of fluoxymesterone, 4-chlorodehydromethyltestosterone, stanozolol and danazol. Factors affecting the extraction process were studied and a novel LPME method with in-fiber silylation was developed and validated for GC/MS analysis of the danazol metabolite. The method allowed precise, selective and sensitive analysis of the metabolite and enabled simultaneous filtration, extraction, enrichment and derivatization of the analyte from urine without any other steps in sample preparation. Liquid chromatographic/tandem mass spectrometric (LC/MS/MS) methods utilizing electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) were developed and applied for detection of oxandrolone and metabolites of stanozolol and 4-chlorodehydromethyltestosterone in urine. All methods exhibited high sensitivity and specificity. ESI showed, however, the best applicability, and a LC/ESI-MS/MS method for routine screening of nine 17-alkyl-substituted AAS was thus developed enabling fast and precise measurement of all analytes with detection limits below 2 ng/ml. The potential of chemometrics to resolve complex GC/MS data was demonstrated with samples prepared for AAS screening. Acquired full scan spectral data (m/z 40-700) were processed by the OSCAR algorithm (Optimization by Stepwise Constraints of Alternating Regression). The deconvolution process was able to dig out from a GC/MS run more than the double number of components as compared with the number of visible chromatographic peaks. Severely overlapping components, as well as components hidden in the chromatographic background could be isolated successfully. All studied techniques proved to be useful analytical tools to improve detection of AAS in urine. Superiority of different procedures is, however, compound-dependent and different techniques complement each other.

Muusikon mentaaliharjoittelu : Konsertoivan ja opettavan pianistin mentaaliharjoittelu

This research explores the foci, methods and processes of mental training by pianists who are active as performers and teachers. The research is based on the concept of mental training as a solely mental mode of practising. Musician s mental training takes place without an instrument or the physical act of playing. The research seeks answers to questions: 1) What are the foci of a pianist s mental training? 2) How does a pianist carry out the mental training? 3) What does mental training in music entail as a process? The research approach is qualitative, and the materials were gathered from thematic interviews. The aim of practising is always an improved result both in the act of playing and the performance. Mental training by a pianist is collaboration between technical, auditory, visual, kinaesthetic and affective factors. Also interpretation, memory and overcoming stage fright are needed. Technical, cognitive and performance skills are involved. According to the results of this research, mental training is a goal-oriented activity which can have an impact on all of these factors. Without a musical inner ear and its functionality, true musicianship cannot exist. One particular result of this research is the conceptualisation of opening up the inner ear. Auditory exercises and internally playing mental images are essential elements of the mental practice of a musician. Visual images, such as a picture of music notation or a performance event, are the point of focus for musicians who find visual images to be the easiest to realise. When developing technical skills by using mental training, it is important to focus on the technically most difficult sections. It is also necessary to focus on the holistic experiencing of the performance situation. By building on positive energies and strengths, the so-called psyching up may be the most important element in mental training. Based on the results of this research, a synthesis is outlined of the music event as an activity process, built on representations and schemes. Mental training aims at the most ideal possible act of playing and the creation of a musical event; these are achieved by focussing on various mental images produced by the different senses, together with concrete practising. Mental training in sports and in music share common factors. Both modes of practising, mental as well as physical, involve three important elements: planning, realisation and evaluation of the practice. In music, however, the goal is an artistic end result which does not often apply to an athletic event. Keywords: Mental training in music, auditory imagining, visualisation, kinaesthetic-mental experience, mastery of the psyche