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McIlwain was born on 20 December 1912 in Newcastle upon Tyne. He was educated at King's College, Durham University 1930-1936 (B.Sc. in Chemistry 1934, M.Sc., Ph.D. 1936) and spent the year 1936-1937 at Queen's College, Oxford researching the organic chemistry of natural products. During the period 1937-1945 he was Leverhulme Research Fellow in the Medical Research Council (MRC) Department of Bacterial Chemistry, and subsequently member of the scientific staff of the MRC, at the Middlesex Hospital Medical School and subsequently at Sheffield University. During the period 1945-1947 he was Lecturer in Biochemistry, Sheffield University and member of the scientific staff of the MRC and of the Council's Unit for Cell Metabolism, Department of Biochemistry, Sheffield University. In 1948 he moved to the Maudsley Hospital as Senior Biochemist in the Teaching and Research Laboratories and subsequently Senior Lecturer and then Reader in Biochemistry in the University of London at the Institute of Psychiatry. In 1954 he was appointed Professor of Biochemistry in the University of London at the Institute of Psychiatry (Professor Emeritus 1980). He was then Visiting Professor, Department of Biochemistry, St Thomas's Hospital Medical School, London, continuing research supported by the MRC, 1980-1986. After moving to Shropshire in 1986 McIlwain was based for his residual academic activities at the University of Birmingham Medical School.
McIlwain's early research career in association with P.G. Fildes at the Middlesex Hospital and H.A. Krebs in Sheffield focused on nutritional factors controlling the growth of bacteria and synthetic bacterial antimetabolites as chemotherapeutic agents for treating bacterial infection. His post-war move to the Maudsley Hospital and the Institute of Psychiatry was a marked change of direction. Here he organised a department dealing with biochemical research on the nervous system and the teaching of neurochemistry to postgraduate medical students. His research and teaching programmes, his textbooks and his active role in the establishment of the Journal of Neurochemistry (1956) and the International Society for Neurochemistry (1967) distinguish him as one of the founding fathers of the modern discipline. In retirement he devoted much time to his interests in the history of science and neurochemistry in particular. He died on 14 September 1992.