History of Research on Soy-Related Enzymes and Others (1802-2021)

William Shurtleff, Akiko AoyagiISBN: 978-1-948436-61-8

Publication Date: 2021 Dec. 10

Number of References in Bibliography: 2332

Earliest Reference: 1802

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Brief Chronology of Research on Enzymes

1755 – The word “ferment” is first used as a noun – as we would later use the word “enzyme” – in Samuel Johnson’s Dictionary of the English Language. “the ferment put into drink to make it work; and into bread to make it lighten and swell.”

1833 – Diastase (a mixture of amylases) is the first enzyme to be discovered (Armstrong 1933).

1836 – The concept of catalysts, chemicals facilitating a reaction without undergoing any change themselves, is introduced by Berzelius who quickly hypothesized that enzymes were such catalysts.

1838 – The word “diastase” is first used in print in English – Merriam-Webster’s Dictionary.

1877 – The term enzyme is first coined by Wilhelm Kűhne in German (Verhandlungen Des Naturhistorisch-Medicinischen Vereins Zu Heidelberg, 1877, p. 190-193).

1877 – The word “proteolytic” is first used in print in English – Merriam-Webster’s Dictionary.

1881 May 5 – The word “enzyme” is first used in print in English – Oxford English Dictionary.

William Roberts (in England) writes in the Proceedings of the Royal Society of London – 32(313):145-61: “The term ferment has, up to this time, been applied in common to two groups of agents, which, although nearly allied both in their origin and in their mode of action, belong to distinct categories. The organised or formed ferments, of which yeast is the type, are independent organisms with powers of growth and reproduction... The soluble ferments, on the other hand, pass freely into solution in water - their action is dissociated from the life of the gland-cells which produced them – and they are wholly devoid of the power of growth and reproduction.

“Kühne has proposed to distinguish the group of soluble ferments by the name of ‘enzyms.’ I would suggest the desirability of adopting this [German] term into English, with a slight change of orthography, as 'enzymes,' and also of coining from this root the cognate words which are requisite for clear and concise description. The action of an enzyme may be designated enzymosis, and the nature of the action may be spoken of as enzymic.”

1881 May 12 – R.W. Atkinson (at the University of Tokio, Japan) writes “On the diastase of kōji” in the Proceedings of the Royal Society of London – 32(312):299-332.

1883 – The word “amylase” is first used in print in English – Merriam-Webster’s Dictionary.

1894 – The lock and key model of enzyme action is introduced (Heckmann & Paradisi 2020).

1897 – The word “lipase” is first used in print in English – Merriam-Webster’s Dictionary.

1897 – Franz Lafar (of Germany) in his Technische Mykologie. Ein Handbuch der Gärungsphysiologie... Erster Band: Schizomyceten-Gärungen [Technical mycology. A handbook of fermentation physiology... Vol. 1: Schizomycetic fermentations], is the first to describes the action of enzymes produced during soybean fermentations (of natto and miso) – without using the German word for “enzyme.” Instead he uses the German words Mikrozymen and Mikrozyma (microzymes).

1898 Sept. – An early use of the word “enzyme” appears in an article by Stone & Wright, who write, in “Notes on taka-diastase”: "There has recently come into notice, chiefly through its industrial applications, a starch-saccharifying enzyme of apparently unusual value. This substance, called taka-diastase, has been in use in Japan for an indefinite time in the production of alcoholic beverages in much the same capacity as that for which we employ malt. Its introduction to America is due to Mr. Jokichi Takamine, who for some years has been occupied in furthering its application in the distilling industry in the United States. (Journal of the American Chemical Society – 20(9):639-47).

1903 – The word “protease” is first used in print in English – Merriam-Webster’s Dictionary.

1909 – The presence of high amounts of urease in crude extracts of soy bean seeds and seedlings is discovered by T. Takeuchi of Japan (“On the occurrence of urease in higher plants.” Journal of the College of Agriculture, Tokyo Imperial University 1(1):1-14). June 16).

1926 – It is discovered that enzymes are proteins (Heckmann & Paradisi 2020).

1930 Feb. – J.R. Short Milling Co. of Chicago starts to make and sell Wytase, the first enzyme-active soy flour used for natural bleaching of bread and other baked goods. The process was discovered by Louis W. Haas and his co-worker Ralph M. Bohn, in the research laboratories of The W.E. Long Company in Chicago. The research work had been undertaken under contract for Mr. J.R. Short, president of the J.R. Short Milling Co. of Chicago; his company now has the rights to manufacture, control, and sell the new natural bleaching substance (Food Industries, Feb. 1930, p. 57-59).

1942 Nov. – The word “lipoxidase” is first used in English – in the title of an article and in connection with soy beans – by Robert J. Sumner who writes: The oxidizing factor was identified as the enzyme lipoxidase, the existence of which was first noted by André and Hou (1932). (“Lipid oxidase studies. II. The specificity of the enzyme lipoxidase.” J. of Biological Chemistry. 146(1):211-13).

1950 Oct. 10 – The earliest document seen that mentions the term “enzyme-active” in connection with soybeans is U.S. Patent No. 2,254,991 titled “Process of preparing soybean meal” issued to Herbert Otto Renner.

1952 – Plasmids are discovered (Heckmann & Paradisi 2020).

1958 – The structure of protein is first reported (Heckmann & Paradisi 2020).

1967 Jan. – The word “lipoxygenase” is first used in English – in the title of an article and in connection with soy beans – by Mitsuda et al. of Japan (Agricultural and Biological Chemistry 31(1)115-18.)

1967 Dec. – Wilkens, Mattick and Hand at Cornell University discover that the enzyme lipoxidase causes off-flavors in soymilk and soy flours.

The authors found, by means of sophisticated chemical-analytical techniques (especially chromatography), that the enzyme lipoxidase, which is present in whole soybeans, is the cause of the beany flavor in soymilk. The off-flavors are not present in the whole dry soybeans but are formed during processing. As soon as the soaked or dry soybeans are ground with water at a temperature below 80°C (180°F) (or the tissues of the soybean cotyledons are broken or damaged in any way in the presence of even a small amount of moisture), the lipoxidase enzyme almost immediately catalyzes off-flavor development by acting on the lipids (oils and fats) in the soybeans. In particular it catalyzes the oxidation of unsaturated fatty acids (principally linoleic and linolenic acids), which results in rancidity and off-flavor formation, and produces more than 80 compounds called volatiles, all having low molecular weights. The majority of these volatiles are reported to be ketones, aldehydes, and alcohols, and most impart undesirable flavors.

This discovery started the modern era of good-tasting soymilks.

1969 – Nicholas Catsimpoolas and Martha Kona – working for Central Soya, Chemurgy Division – compile a good bibliography with 162 references titled “Soybean seed enzymes: A selected list of references, 1914-1968” (C.S. Library List, No. 3. 13 p.).

The references are sorted alphabetically by author. For foreign-language documents, only English-language translations of the title are given (unfortunate). There are no subdivisions.

1975 April – Walter J. Wolf discovers that the enzyme lipoxygenase, acting on the lipids in soybeans, are a major source of objectionable flavors in soybean protein products (J. of .Agricultural and Food Chemistry – 23(2):136-41. March/April).

1981 March – Soybean seed protein electrophoresis profiles from 15 Asian countries or regions: Hypotheses on paths of dissemination of soybeans from China, by Hymowitz and Kaizuma published in Economic Botany – 35(1):10-23. March. This very important and pioneering paper is based in part on the observation that three alleles of the Kunitz trypsin inhibitor are electrophoretically distinguishable from one another by their Rf values. And, the seed protein beta-amylase has 2 alleles, which are electrophoretically distinguishable from one another by their Rf values.

1981 May – Hildebrand and Hymowitz, after screening the USDA soybean germplasm collection, find two soybean genotypes lacking lipoxygenase-1 (J. of the American Oil Chemists’ Society – 58(5):583-86).

1982 July – Inheritance of lipoxygenase-1 activity in soybean seeds, by Hildebrand and Hymowitz is published in Crop Science – 22(4)851-53, July/Aug.

1985 March – “Re-evaluation of the inheritance of urease in soybean seed,” by Kloth and Hymowitz is published in Crop Science – 25(2):352-54. March/April.

1996 fall – Iowa State University releases seed of a “triple null” soybean variety that is lacking the 3 lipoxygenase enzymes (L-1, L-2, and L3) that produce beany flavors. Dr. Walter Fehr (soybean breeder at Iowa State) has made tofu and soymilk using the soybean lacking L-2 found that these products have no detectable beany flavor.

Click here to download the full text to open and read book History of Research on Soy-Related Enzymes and Others (1802-2021)