2
1.3.5 Preparation and Separation of Schardinger Dextrins
24
1.3.6 The Action of Amylases on Cycloamyloses
26
1.3.7 The First Schardinger Dextrin-Related Patents
29
1.3.8 Cyclodextrins as Models
30
1.3.9 Complex Formation and Inclusion Compounds
33
1.3.10 The First Reviews on Schardinger Dextrins
38
1.3.11 Toxicological Considerations
39
1.3.12 Other Works During the Period from 1911 to 1970
40
1.4 Historical Landmarks in the Development of Cyclodextrins: From 1970 Until Now
45
1.4.1 Production of Cyclodextrins
45
1.4.2 Mechanism of Inclusion Complexes
46
1.4.3 Inclusion Phenomena and Its Effects
49
1.4.4 Large Cyclodextrins
49
1.4.5 First Comprehensive Reviews on Cyclodextrins
50
1.4.6 First Books on Cyclodextrins
52
1.4.7 The Dissemination of Knowledge About Cyclodextrins
53
1.4.8 The First International Cyclodextrin Symposium
53
1.4.9 Cyclodextrin Derivatives
54
1.4.10 The First Applications of Cyclodextrins
56
1.4.11 Cyclodextrins: Trends and Outlook
66
1.5 Conclusion
69
References
70
Abstract Cyclodextrins are cyclic oligosaccharides obtained by enzymatic degradation of starch. They are remarkable macrocyclic molecules that have led major
theoretical and practical advances in chemistry, biology, biochemistry, health science, and agriculture. Their molecular structure is composed of a hydrophobic cavity that can encapsulate other substances to form inclusion complexes through
host-guest interactions. This unique feature is at the origin of many applications.
Cyclodextrins and their derivatives have a wide variety of practical applications in
almost all sectors of the industry, including pharmacy, medicine, foods, cosmetics,
chromatography, catalysis, biotechnology, and the textile industry.
Villiers published the first reference to cyclodextrins in 1891. Since the beginning of the twentieth century, major researchers, such as Schardinger, Pringsheim,
Karrer, Freudenberg, French, Cramer, Casu, Bender, Saenger, Nagai, Szejtli, and
Pitha, have paved the history of the cyclodextrins. Several time periods have marked
their history. After their discovery and characterization from 1891 to 1911, there has
been a period of doubt and disagreement from 1911 to 1935. Then, the 1935–1950
exploration period was marked by structural results on the “Schardinger dextrins.”
In 1949, Cramer introduced the cyclodextrin-based nomenclature. Research
between 1950 and 1970, the period of maturation, focused on conformations and
spectroscopic data of cyclodextrins and their inclusion complexes, with applications
in catalysis and as enzyme models. Finally, the period of use has been ongoing since
1970 and has seen cyclodextrins find many industrial applications. Cyclodextrins
have then found many industrial applications, initially in the pharmaceutical and
food sectors. In 1984, the first chromatographic columns were commercialized.
At that time, many cyclodextrin-based catalysts were developed for biomimetic
N. Morin-Crini et al.
1.3.5 Preparation and Separation of Schardinger Dextrins
24
1.3.6 The Action of Amylases on Cycloamyloses
26
1.3.7 The First Schardinger Dextrin-Related Patents
29
1.3.8 Cyclodextrins as Models
30
1.3.9 Complex Formation and Inclusion Compounds
33
1.3.10 The First Reviews on Schardinger Dextrins
38
1.3.11 Toxicological Considerations
39
1.3.12 Other Works During the Period from 1911 to 1970
40
1.4 Historical Landmarks in the Development of Cyclodextrins: From 1970 Until Now
45
1.4.1 Production of Cyclodextrins
45
1.4.2 Mechanism of Inclusion Complexes
46
1.4.3 Inclusion Phenomena and Its Effects
49
1.4.4 Large Cyclodextrins
49
1.4.5 First Comprehensive Reviews on Cyclodextrins
50
1.4.6 First Books on Cyclodextrins
52
1.4.7 The Dissemination of Knowledge About Cyclodextrins
53
1.4.8 The First International Cyclodextrin Symposium
53
1.4.9 Cyclodextrin Derivatives
54
1.4.10 The First Applications of Cyclodextrins
56
1.4.11 Cyclodextrins: Trends and Outlook
66
1.5 Conclusion
69
References
70
Abstract Cyclodextrins are cyclic oligosaccharides obtained by enzymatic degradation of starch. They are remarkable macrocyclic molecules that have led major
theoretical and practical advances in chemistry, biology, biochemistry, health science, and agriculture. Their molecular structure is composed of a hydrophobic cavity that can encapsulate other substances to form inclusion complexes through
host-guest interactions. This unique feature is at the origin of many applications.
Cyclodextrins and their derivatives have a wide variety of practical applications in
almost all sectors of the industry, including pharmacy, medicine, foods, cosmetics,
chromatography, catalysis, biotechnology, and the textile industry.
Villiers published the first reference to cyclodextrins in 1891. Since the beginning of the twentieth century, major researchers, such as Schardinger, Pringsheim,
Karrer, Freudenberg, French, Cramer, Casu, Bender, Saenger, Nagai, Szejtli, and
Pitha, have paved the history of the cyclodextrins. Several time periods have marked
their history. After their discovery and characterization from 1891 to 1911, there has
been a period of doubt and disagreement from 1911 to 1935. Then, the 1935–1950
exploration period was marked by structural results on the “Schardinger dextrins.”
In 1949, Cramer introduced the cyclodextrin-based nomenclature. Research
between 1950 and 1970, the period of maturation, focused on conformations and
spectroscopic data of cyclodextrins and their inclusion complexes, with applications
in catalysis and as enzyme models. Finally, the period of use has been ongoing since
1970 and has seen cyclodextrins find many industrial applications. Cyclodextrins
have then found many industrial applications, initially in the pharmaceutical and
food sectors. In 1984, the first chromatographic columns were commercialized.
At that time, many cyclodextrin-based catalysts were developed for biomimetic
N. Morin-Crini et al.