International Journal of Mass Spectrometry 316–318 (2012) 2–4
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Personal Foreword
Alexander George Harrison
Alex Harrison is enjoying a long and distinguished research career in mass spectrometry. On the occasion of this gentleman’s 80th birthday, we would like to interrupt his studies to pay tribute to his remarkable contributions to knowledge and understanding in the field of mass spectrometry. We mention without comment that the 80th birthday fell on April Fool’s Day again this year! Since 2001 when Alex turned 70, an age when many scientists hang up their labcoats, he has published over 30 papers in high-impact journals. More of that later, but it is worth noting that he still holds a research grant from NSERC (roughly the Canadian equivalent of the NSF in the US) and is sought after as a collaborator by new generations of researchers.
continuous scanning, otherwise the magnet current was adjusted stepwise manually and galvanometer readings of the corresponding detector outputs were recorded by hand. The essential tool kit of the mass spectrometrist included a glass-blowing torch, soldering irons of various shapes and sizes, and a good quality test-meter. Keeping the contraption working was a significant part of the graduate student’s duties. Alex has never demonstrated anything resembling masochistic tendencies, so it must have been the enthusiasm and character of Harry Thode that convinced him that mass spectrometry was for him. Because of the inherently slow response times and scan speeds available, applications of mass spectrometry in those days were quite limited compared to today. The positive side of this limitation was that one was forced to think very carefully about what one was going to do in the next experiment. Meticulous planning and persistent experimentation in pursuit of a well-defined chemical question have been the hallmark of Alex Harrison’s work throughout his career, no doubt reflecting his own character but surely also partly the result of lessons learned in his early days in the McMaster basement (mass spectrometers always seemed to be relegated to basements until relatively recently!).
Alex in his M.Sc. days in 1953, with Professor Christian Sivertz, University of Western Ontario The use of the word ‘long’ in our opening sentence demands some explanation. After earning his B.Sc. and M.Sc. at the University of Western Ontario, Alex started his long journey in mass spectrometry in 1953 when he signed on for a Ph.D. program at McMaster University. His Ph.D. Advisor was Harry Thode, one of the pioneers of our discipline and President and Vice-Chancellor of McMaster University from 1961 to 1972. In those days, mass spectrometers were home-built magnetic sector contraptions made of metal and glass, often involving all-glass vacuum systems with mercury diffusion pumps, glass-metal seals, and requiring liberal use of Picene wax for temporary plugging of leaks detected using a Tesla coil. Electron ionization was the only option for chemical applications. Vacuum-tube electronics were a far cry from the sophisticated solid-state controls of today. If one was fortunate the spectral output was recorded on a strip-chart recorder for 1387-3806/$ – see front matter © 2012 Published by Elsevier B.V. http://dx.doi.org/10.1016/j.ijms.2012.04.002
The life of a Ph.D. student in 1956 was a hard one. Alex’s thesis was titled “Isotope Effects in the Reduction of Sulphur Compounds”. It took him only 3 years to complete his Ph.D. program, so he stayed on at McMaster for an extra year as a postdoctoral fellow. Five papers were published out of this work, with applications ranging from “Sulphur Isotope Abundances in Hydrocarbons and Source Rocks of Uinta Basin, Utah” to “Mechanism of the Bacterial Reduction of Sulphate from Isotope Fractionation Studies”. Nothing if not eclectic! Then in 1956 Alex moved to a
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postdoctoral fellowship at the National Research Council in Ottawa to work with Fred Lossing, another major figure in the early days of chemical mass spectrometry, who specialized in precise measurements of heats of formation of gas-phase ions and radicals. In 1958, after two productive years and 10 papers in Ottawa, Alex was appointed to a temporary Lecturer position in the Chemistry Department at the University of Toronto. The following year, in one of that Department’s smarter moves, Alex was appointed as a tenure-track Assistant Professor whereupon he moved rapidly up the promotion ladder to become a Full Professor in 1967. Naturally, on becoming an independent scientist Alex felt obliged to move out of the considerable shadows cast by Harry Thode and Fred Lossing, and to find his own niche. It is dangerous to try to summarize a research record in a single phrase, but a common thread through most of his 265 independent papers consists of careful determinations of structures and reaction mechanisms of gas-phase organic ions. This program involved both investigations of specific ions and families of ions and development of new methodologies. For example, in the early 1970s he devised an ingenious technique for trapping ions and studying their reactions on a millisecond timescale using a modified electron ionization magnetic sector mass spectrometer. Briefly, primary reactant ions, produced by an electron beam pulse of about 1 s duration and 10-50 eV nominal electron energy, were trapped in the negative space charge of a continuous electron beam of about 5 eV energy and 8 A trap current. The ions could be trapped for periods up to 2 ms permitting the study of the reactions not only of primary ions but of products formed in the primary reactions. A low background pressure of reactant gas permitted studies of ion/molecule reactions well before the wide introduction of ion trap instruments. Ions were removed for mass analysis by applying a positive pulse of 5 V amplitude and 4 s duration to the repeller electrode. Absolute rate coefficients and relative rate coefficients were obtained for molecular ions of, for example, methane, ethylene, acetylene, methyl fluoride, and methyl chloride; the results indicated that the reactant ions had kinetic energies in the range 0.3 to 0.5 eV. Alex was one of the first to realize the possibilities of a chemical ionization ion source as a reaction vessel for his own research interests, as well as for more routine analytical applications. His classic text on Chemical Ionization Mass Spectrometry was first published in 1983, and a considerably enlarged second edition in 1992. These studies of what we would nowadays call small organic ions paved the way for what has turned out to be a second career that commenced with his appointment as Professor Emeritus in 1993. In 1995 and 1996, he published two seminal papers concerning the structures of b-type fragment ions from peptides. From that point on, Alex focused his attention on peptide ions. With more than 30 papers published on peptide ions, Alex’ work has attracted
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the attention of much younger collaborators including some specializing in high-level quantum chemistry calculations of reaction pathways. The meticulous results reported by Alex are regarded as the gold standard for comparison of such calculations with experiment. Alex has an impressive list of formal distinctions. He was an Alfred P. Sloan Fellow from 1962-64, and a Killam Research Fellow from 1985-87. He was the first Canadian to be elected to the Board of the American Society for Mass Spectrometry. His home Department at the University of Toronto established the Alex Harrison Graduate Fellowship in Analytical Environmental Mass Spectrometry in 2005, and he has been a guest lecturer and distinguished visiting scientist at several institutions.
Alex presenting the 2010 Alex Harrison Graduate Scholarship in Environmental Analytical Mass Spectrometry to Rachel Chang On a more personal note, in 1984 the Gang of Three (Alex Harrison, Ray March and Bob Boyd) were awarded funds by NSERC to purchase a new instrument, a hybrid consisting of a doublefocusing analyzer of reverse geometry with a linear quadrupole in tandem, designed for ion structure studies. This rather large machine was installed in Alex’ laboratories at Toronto where it was maintained properly and made available for the research programs of the others. It will surprise no-one who knows him, particularly his former students and postdoctoral fellows, to learn that the time and facilities thus provided were always flexible and generous.
Alex with the new ZAB-BEqQ instrument console in 1986, figuring out which knob is which.
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So now he is 80, perhaps not quite the energetic dynamo of decades back but still very much in the game with a winning record. A conventional tribute would end with best wishes for a long and happy retirement with Barbara, his children and grandchildren, but Alex shows few if any signs of wanting to retire. He’s having too much fun with all of the above.
Alex with his first grandchild, 1991.
Robert K. Boyd Researcher Emeritus, National Research Council of Canada, Vancouver, BC, Canada Raymond E. March Professor Emeritus, Department of Chemistry, Trent University Peterborough, ON, Canada