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The development of a mass spectrometer can be traced back to the late 19th cen-

tury, when Sir Joseph J. Thomson used a vacuum tube to measure the charge-to- mass ratio of cathode rays, and was awarded the Nobel Prize in Physics in 1906 ”in recognition of the great merits of his theoretical and experimental investiga-

tions on the conduction of electricity by gases.”1 However, Thomson’s curiosity about the electrical discharge behaviors originated from the discovery of ”Kanal- strahlen” (canal rays) by Eugene Goldstein at Berlin Observatory (Watson and

Sparkman, 2008). Figure 2.1 (Beynon and Morgan, 1978) shows his apparatus for such measurement, in which the letter ”M” means the magnet that generates

1_{See http://www.nobelprize.org/nobel prizes/physics/laureates/1906/ for information about}

a magnetic field perpendicular to the plane of Fig. 2.1.

Figure 2.1: Sir Joseph J. Thomson’s apparatus for measuring the charge-to- mass ratio of cathode rays (Beynon and Morgan, 1978).

The discovery and research of isotopes are also widely recognized as milestones

in the mass spectrometry history. In particular, Frederick Soddy and Francis W. Aston received their Nobel Prizes in Chemistry in 1921 and 1922, respectively, for Soddy’s ”contributions to our knowledge of the chemistry of radioactive sub-

stances, and his investigations into the origin and nature of isotopes,”2 and for Aston’s ”discovery, by means of his mass spectrograph, of isotopes, in a large number of non-radioactive elements, and for his enunciation of the whole-number

rule.”3 Figure 2.2 (Watson and Sparkman, 2008) shows the mass spectrometer designed by Aston.

The oil drop experiment performed in 1909 leads Robert A. Millikan to the

Nobel Prize in Physics in 1923 for his ”work on the elementary charge of electric- ity and on the photoelectric effect.”4 _{Some believe that the oil drop experiment} can be considered the first example of the electrospray ionization (ESI) method,

2_{See http://www.nobelprize.org/nobel prizes/chemistry/laureates/1921/ for information}

about the Nobel Prize in Chemistry 1921, accessed 10 August 2012.

3_{See http://www.nobelprize.org/nobel prizes/chemistry/laureates/1922/ for information}

about the Nobel Prize in Chemistry 1922, accessed 10 August 2012.

4_{See http://www.nobelprize.org/nobel prizes/physics/laureates/1923/ for information about}

Figure 2.2: Replica of Francis W. Aston’s third mass spectrometer, commis- sioned by the American Society for Mass Spectrometry (Watson and Sparkman, 2008).

which is now a widely used ionization method for MS. A U.S. patent was granted to Ernest O. Lawrence in 1934 for the invention of the cyclotron (Lawrence, 1934), and later in 1939 the Nobel Prize in Physics was awarded to Lawrence ”for the

invention and development of the cyclotron and for results obtained with it, espe- cially with regard to artificial radioactive elements.”5 _{Figure 2.3 (Lawrence and} Livingston, 1932) shows the ion acceleration apparatus developed by Lawrence.

The cyclotron concept was later adapted, and in 1974 the mass analysis method of Fourier-transform ion cyclotron resonance (FT-ICR) was invented by Comisarow and Marshall (Comisarow and Marshall, 1974a).

Although it was not until 1989 that the next MS related Nobel laureates of Hans G. Dehmelt and Wolfgang Paul were recognized (one half awarded in Physics) ”for the development of the ion trap technique,”6 _{the interests toward}

the MS related topics remained active in between the Nobel ”gap years” (Wat-

5_{See http://www.nobelprize.org/nobel prizes/physics/laureates/1939/ for information about}

the Nobel Prize in Physics 1939, accessed 10 August 2012.

6_{See http://www.nobelprize.org/nobel prizes/physics/laureates/1989/ for information about}

(a)Photo of the vacuum tube with cover removed.

(b)Apparatus diagram.

Figure 2.3: Apparatus for the multiple acceleration of ions, invented by Lawrence (Lawrence and Livingston, 1932).

son and Sparkman, 2008). One of the evidences can be found in the MS review paper written by Hipple and Shepherd and published in the journal of Analytical Chemistry in 1949 (Hipple and Shepherd, 1949), in which 176 references were

cited. Later in 1998, another MS review paper in Analytical Chemistry writ- ten by Burlingame and co-workers became a 70-page report with 1409 citations

(Burlingame et al., 1998).

Later, in 1996 Robert F. Curl Jr., Sir Harold W. Kroto, and Richard E. Smalley were awarded the Nobel Prize in Chemistry in 1996 ”for their discovery

of fullerenes,”7 where the C60 signal was first recorded by a time-of-flight (TOF) mass spectrometer in 1985 (Kroto, 1997). The Nobel Prize in Chemistry 2002 was received ”for the development of methods for identification and structure

analyses of biological macromolecules.”8 Whilst one half of the prize was for the development of the nuclear magnetic resonance (NMR) spectroscopy method, the other half went jointly to John B. Fenn and Koichi Tanaka ”for their development

of soft desorption ionization methods for mass spectrometric analyses of biological macromolecules,”8 _{in which the ionization techniques of ESI and matrix-assisted} laser desorption/ionization (MALDI) were developed.

Nowadays, there are many good references about the history of MS. The re- view sections and book sections/chapters mentioned in this thesis can be excellent starting points for researchers to investigate further.

7_{See http://www.nobelprize.org/nobel prizes/chemistry/laureates/1996/ for information}

about the Nobel Prize in Chemistry 1996, accessed 10 August 2012.

8_{See http://www.nobelprize.org/nobel prizes/chemistry/laureates/2002/ for information}